JP2989506B2 - Prepreg and its FRP products - Google Patents

Prepreg and its FRP products

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Publication number
JP2989506B2
JP2989506B2 JP2699295A JP2699295A JP2989506B2 JP 2989506 B2 JP2989506 B2 JP 2989506B2 JP 2699295 A JP2699295 A JP 2699295A JP 2699295 A JP2699295 A JP 2699295A JP 2989506 B2 JP2989506 B2 JP 2989506B2
Authority
JP
Japan
Prior art keywords
prepreg
fiber
component
tonf
fibers
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
Application number
JP2699295A
Other languages
Japanese (ja)
Other versions
JPH08217896A (en
Inventor
栄記 伊藤
朋宏 中西
幹人 牧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Nippon Steel Corp
Original Assignee
Shin Etsu Chemical Co Ltd
Nippon Steel Corp
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Filing date
Publication date
Application filed by Shin Etsu Chemical Co Ltd, Nippon Steel Corp filed Critical Shin Etsu Chemical Co Ltd
Priority to JP2699295A priority Critical patent/JP2989506B2/en
Publication of JPH08217896A publication Critical patent/JPH08217896A/en
Application granted granted Critical
Publication of JP2989506B2 publication Critical patent/JP2989506B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【産業上の利用分野】本発明はプリプレグに係わり、特
に弾性率が低く、軽量で、加工性に優れ、かつ熱的特性
に優れたプリプレグ及びそのFRP製品に関するもので
ある。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a prepreg, and more particularly to a prepreg having a low elastic modulus, light weight, excellent workability, and excellent thermal properties, and an FRP product thereof.

【0002】[0002]

【従来の技術】強化繊維と樹脂とからなる繊維強化プラ
スチックス(以下FRPと略記)は、比強度、比弾性
率、化学的安定性等に優れている為、釣竿、ゴルフクラ
ブ等のスポーツ・レジャー用品や板バネ、ロール類やハ
ニカム構造材等の工業材料、さらには自動車用、航空機
用、或いは医療材料等の製品素材として成形材料の分野
で広く利用されている。そしてFRP製品の素材として
は、強化繊維に樹脂を予め含浸させたいわゆるプリプレ
グを使用する場合が多い。これらのFRP製品の特性
は、使用するプリプレグの強化繊維および樹脂の種類や
量さらには強化繊維と樹脂との化学的、機械的接着性に
依存することは周知の事実であるが、炭素繊維を強化繊
維として使用する場合、比較的弾性率の高い、具体的な
弾性率で示すならば8tonf/mm2以上の長繊維炭素繊維が
これまでは使用されてきた。
2. Description of the Related Art Fiber reinforced plastics (hereinafter abbreviated as FRP) comprising reinforced fibers and resins are excellent in specific strength, specific elastic modulus, chemical stability and the like, and are used for sports poles such as fishing rods and golf clubs. It is widely used in the field of molding materials as leisure materials, industrial materials such as leaf springs, rolls, and honeycomb structural materials, as well as product materials such as automobiles, aircraft, and medical materials. As a material of the FRP product, a so-called prepreg in which a reinforcing fiber is impregnated with a resin in advance is often used. It is a well-known fact that the properties of these FRP products depend on the type and amount of the reinforcing fiber and resin of the prepreg to be used, and also on the chemical and mechanical adhesion between the reinforcing fiber and the resin. When used as a reinforcing fiber, a long-fiber carbon fiber having a relatively high modulus of elasticity, specifically, 8 tonf / mm 2 or more when expressed by a specific modulus of elasticity has been used.

【0003】FRP製品は、最初ガラス繊維を強化繊維
とするGFRPから出発したが、ガラス繊維は比重が
2.54と高く、かつ引張弾性率が約7tonf/mm2と低い
ことから、より軽量でかつ引張弾性率の高い炭素繊維を
強化繊維とするCFRP製品へと移行してきた。このよ
うな比重がガラス繊維よりも低くかつ引張弾性率が8to
nf/mm2以上の強化繊維を使用した例としては、例えば特
開昭49−91877号、特開昭59−104931
号、特公平3−16086号等が開示されている。この
ようにプリプレグを使用してFRP製品を製造する場
合、これまでは比較的弾性率の高い、具体的な弾性率で
示せば8tonf/mm2以上の長繊維炭素繊維を1種類或いは
2種類以上が必要に応じて適宜組み合わせて使用されて
きた。
[0003] FRP products started from GFRP using glass fiber as a reinforcing fiber, but the glass fiber has a higher specific gravity of 2.54 and a tensile modulus of as low as about 7 tonf / mm 2 , so that it is lighter. In addition, there has been a shift to CFRP products using carbon fibers having a high tensile modulus as reinforcing fibers. Such specific gravity is lower than glass fiber and tensile modulus is 8 to
Examples using reinforcing fibers of nf / mm 2 or more include, for example, JP-A-49-91877 and JP-A-59-104931.
And Japanese Patent Publication No. 3-16086. In the case where an FRP product is manufactured using a prepreg in this way, one or two or more types of long-fiber carbon fibers having a relatively high elasticity and a specific elasticity of 8 tonf / mm 2 or more can be used. Have been used in combination as needed.

【0004】これらは比較的剛性の高いFRP製品には
有効であり、比較的弾性率の高い長繊維炭素繊維を組み
合わせて使用することで目的とするFRP製品を得るこ
とができていたが、最近、従来よりも剛性の低いFRP
製品や、部位により剛性の違うFRP製品が求められる
ようになってきた。このような剛性の低いFRP製品と
しては例えば、ゴルフのシャフトや、釣竿、ベッドの床
板等が挙げられる。
[0004] These are effective for relatively rigid FRP products, and the desired FRP products could be obtained by using a combination of long fiber carbon fibers having a relatively high elastic modulus. , FRP with lower rigidity than before
FRP products having different stiffness depending on products and parts have been required. Such low rigidity FRP products include, for example, golf shafts, fishing rods, bed plates, and the like.

【0005】かかる剛性の低いFRP製品が求められる
背景としては、最近増加しつつある女性ゴルファーや、
加齢による体力の衰えた男性ゴルファー等が、比較的剛
性の低いゴルフシャフトのしなり(たわみ)を利用して
飛距離を伸ばすことを目的として利用する為である。
又、最近ではゴルフクラブの番手毎の設計がなされ、番
手毎に、シャフトのたわみやすい部位が異なるシャフト
等が使用されるようになってきており、この場合、シャ
フトのたわみやすい部位に比較的弾性率の低い強化繊維
を使用したプリプレグが使用されるようになってきた。
[0005] The demand for such low rigidity FRP products is due to the increasing number of female golfers,
This is because a male golfer or the like whose physical strength has deteriorated due to aging is used for the purpose of extending the flight distance by using the bending (flexure) of a golf shaft having relatively low rigidity.
In recent years, golf clubs have been designed for each count, and for each count, shafts or the like where the easily bendable portion of the shaft is different have been used. In this case, the easily bendable portion of the shaft is relatively elastic. Prepregs using low-strength reinforcing fibers have been used.

【0006】又、釣竿の場合、初心者は魚がかかると一
気につり上げようとする傾向があるが、この場合、釣竿
の剛性が高いと釣り針に一気に荷重がかかり、魚を傷つ
けたり逃がしたりし易いという欠点があった。さらに、
個々人の好みにもよるが、剛性の比較的高い竿よりも、
比較的弾性率の低いプリプレグを使用した剛性の比較的
低い竿のほうが、天然の竹竿にその感触が近いことから
好まれる傾向がある。しかし現状ではこのような比較的
剛性の低い竿は比重の高いガラス繊維を強化繊維として
しているために重くなり易いという欠点もあった。さら
に、ベッドの床板の場合、個人の好みにもよるが、剛性
が高すぎると疲れが回復しにくいのに対し、比較的剛性
の低い床板を使用することにより床板をたわませ、身体
への負担を軽減させたり、心地良い睡眠を得ることがで
きる。又、このベッドがX線透過用機器の一部である場
合、X線の透過性が高い炭素繊維を強化繊維に使用する
必要がある。
[0006] In the case of a fishing rod, a beginner tends to lift the fish at a stretch when the fish catches. In this case, if the rigidity of the fishing rod is high, a load is applied to the fishing hook at a stretch and the fish is easily damaged or escaped. There were drawbacks. further,
Depending on individual preference, rather than a relatively rigid rod,
A relatively low-rigidity rod using a prepreg having a relatively low elastic modulus tends to be preferred because of its close feel to a natural bamboo rod. However, at present, such relatively low rigidity rods have a drawback that they tend to be heavy because glass rods having high specific gravity are used as reinforcing fibers. Furthermore, in the case of bed floors, depending on personal preference, fatigue is difficult to recover if the rigidity is too high. The burden can be reduced and a comfortable sleep can be obtained. When the bed is part of an X-ray transmission device, it is necessary to use carbon fibers having high X-ray permeability as reinforcing fibers.

【0007】かかる剛性の低いFRP製品の各種の要望
に対しては、引張弾性率の低い材料を使用したり、ある
いは形状をかえることが一般的であるが、従来の引張弾
性率の低い強化繊維を使用したプリプレグでは、プリプ
レグの製造作業性やFRP製品の成形作業性および加工
性に問題があったり、FRP製品の重量が重くなった
り、熱的性質に問題がある等で満足するプリプレグを得
ることができなかった。例えば、弾性率の比較的低い、
具体的な弾性率で示すならば8tonf/mm2未満の強化繊維
としては、ガラス繊維や、アラミド繊維、ポリエチレン
繊維等が知られている。しかしガラス繊維は、炭素繊維
と比較して比重が高く、アラミド繊維は成形後の加工が
しずらいという問題があった。
[0007] In response to various demands for such a low rigidity FRP product, it is common to use a material having a low tensile modulus or change its shape. A prepreg that uses prepreg has satisfactory prepreg manufacturing workability, FRP product molding workability and workability, has a heavy FRP product weight, and has a problem in thermal properties. I couldn't do that. For example, a relatively low modulus of elasticity,
Glass fibers, aramid fibers, polyethylene fibers, and the like are known as reinforcing fibers having a specific elastic modulus of less than 8 tonf / mm 2 . However, glass fibers have a higher specific gravity than carbon fibers, and aramid fibers have a problem that processing after molding is difficult.

【0008】又、ポリエチレン繊維は、比重も軽くまた
加工性についてもさほど問題はないが一般的に耐熱性が
低く、かつ炭素繊維とハイブリッド構造で使用する場
合、炭素繊維と比較して熱膨張係数が高いため、他の炭
素繊維を強化繊維としたプリプレグと併用した場合、F
RP製品にそり等が発生するという問題があり、設計時
にこの点についても注意しなければならないというわず
らわしさがあった。炭素繊維についても弾性率の比較的
低い、具体的な弾性率で示すならば8tonf/mm2未満の強
化繊維がすでに報告されている(日本複合材料学会誌:
第15巻第3号,P.98〜P.103,1989)。
[0008] Polyethylene fiber is low in specific gravity and has no problem in processability, but generally has low heat resistance, and has a higher thermal expansion coefficient than carbon fiber when used in a hybrid structure with carbon fiber. When used in combination with a prepreg using other carbon fibers as reinforcing fibers, F
There is a problem that warpage and the like occur in the RP product, and it is troublesome to pay attention to this point in designing. Carbon fibers have been reported to have a relatively low modulus of elasticity, specifically, a reinforcing fiber of less than 8 tonf / mm 2 if expressed as a specific modulus (Journal of the Japan Society for Composite Materials:
Vol. 15, No. 3, p. 98-P. 103, 1989).

【0009】しかしながら、ここで報告されている弾性
率の比較的低い、具体的な弾性率で示すならば8tonf/m
m2未満の炭素繊維は、その繊維の直径が13〜15μm
と太いために、目付け(単位面積当たりの炭素繊維の重
量)が低いプリプレグが製造しにくかったり、また目付
けの高いプリプレグを使用しても成形時に流れでる樹脂
量が多く、この為樹脂を除去する工程が増加したり、
又、FRP製品の重量の制御が困難である等の問題があ
った。
However, the elastic modulus reported here is relatively low, and the specific elastic modulus is 8 tonf / m
Carbon fiber of less than m 2 has a fiber diameter of 13 to 15 μm
It is difficult to manufacture a prepreg with a low basis weight (weight of carbon fiber per unit area) due to its thickness, and a large amount of resin flows during molding even if a prepreg with a high basis weight is used. Increase the number of processes,
There are also problems such as difficulty in controlling the weight of the FRP product.

【0010】一方形状による剛性の低下方法としては、
厚みを薄くすることや厚みは同じでも強化繊維の使用量
を低減する手法が有効であることが知られている。しか
しながら、例えば釣竿のようなシャフト状のものの
(肉)厚を薄くすると確かに剛性は低下するもののつぶ
し強度(径方向の圧縮強度)が低下するという問題があ
った。又、ゴルフシャフト等の場合、ある部位がたわみ
やすいようにするためにその部分だけの肉厚等を変化さ
せると応力集中がかかりやすくなったり、成形時にボイ
ドが発生しやすくなりこのためこわれやすくなるという
問題があった。肉厚を同じにして使用する強化繊維の使
用量を低下させ、樹脂含有率を増加させたプリプレグを
使用する方法があるが、この場合、成形時に樹脂が流れ
過ぎたり、強化繊維が乱れる等の問題があり好ましい方
法ではない。
On the other hand, as a method of reducing the rigidity by the shape,
It is known that a technique of reducing the thickness and reducing the amount of reinforcing fiber used even when the thickness is the same is effective. However, for example, when the thickness of a shaft-like material such as a fishing rod is reduced, the rigidity is reduced, but the crushing strength (compressive strength in the radial direction) is reduced. Also, in the case of a golf shaft or the like, if the thickness or the like of only a certain portion is changed in order to make a certain portion easily bendable, stress concentration is likely to be applied, and voids are easily generated at the time of molding, so that it is easily broken. There was a problem. There is a method of using a prepreg in which the amount of reinforcing fibers used is reduced by using the same wall thickness and the resin content is increased, but in this case, the resin flows excessively during molding, or the reinforcing fibers are disturbed. There is a problem and it is not the preferred method.

【0011】[0011]

【発明が解決しようとする課題】このように、最近要求
されるようになってきた比較的剛性の低いFRP製品に
対処するには、比較的弾性率の低い長繊維の強化繊維を
使用したプリプレグを用いることが考えられるが、プリ
プレグの製造作業性やFRP製品の成形作業性および加
工性に問題があったり、FRP製品の重量が重くなった
り、熱的性質に問題がある等で未だ満足するプリプレグ
は得られていなかった。従って本発明の目的は、最近要
求されるようになってきた軽量で加工性に優れさらに設
計の自由度が高く比較的剛性の低いFRP製品、あるい
は構造物のある部位で比較的低い剛性に変えたFRP製
品等の成形に好適なプリプレグ及びそのFRP成型品を
提供することである。
As described above, in order to cope with a relatively low rigidity FRP product which has recently been required, a prepreg using a long fiber reinforced fiber having a relatively low elastic modulus is required. However, there is still a problem with the workability of prepreg production, the workability and workability of the molding of the FRP product, the weight of the FRP product becomes heavy, and there is a problem with the thermal properties. No prepreg was obtained. Accordingly, an object of the present invention is to change to a FRP product which has recently been required to be lightweight, has excellent workability, has a high degree of freedom in design, and has a relatively low rigidity, or a relatively low rigidity in a portion of a structure. It is an object of the present invention to provide a prepreg suitable for molding an FRP product or the like and an FRP molded product thereof.

【0012】[0012]

【課題を解決するための手段】本発明者等はかかる課題
を解決するため種々研究した結果、特定のエポキシ樹脂
組成物と長繊維炭素繊維を組み合わせる本発明を完成し
た。すなわち本発明は、下記A、B及びD成分 A:一分子中に少なくとも二個以上のエポキシ基を持つ
ポリエポキシ化合物 B:硬化剤 D:引張弾性率0.4〜7tonf/mm2かつ平均直径11μ
m以下の長繊維炭素繊維を必須成分とし、A及びB成分
を含有するエポキシ樹脂組成物をD成分である強化繊維
に含浸してなることを特徴とするプリプレグである。
Means for Solving the Problems The present inventors have conducted various studies to solve the above problems, and as a result, completed the present invention in which a specific epoxy resin composition and long fiber carbon fiber are combined. That is, the present invention provides the following components A, B, and D: A: a polyepoxy compound having at least two or more epoxy groups in one molecule B: a curing agent D: a tensile modulus of elasticity of 0.4 to 7 tonf / mm 2 and an average diameter 11μ
A prepreg characterized by comprising a long fiber carbon fiber of m or less as an essential component and impregnating a reinforcing fiber as a D component with an epoxy resin composition containing A and B components.

【0013】また下記A、B、C及びD成分 A:一分子中に少なくとも二個以上のエポキシ基を持つ
ポリエポキシ化合物 B:ジシアンジアミド C:硬化促進剤 D:引張弾性率0.4〜7tonf/mm2かつ平均直径11μ
m以下の長繊維炭素繊維を必須成分とし、A、B及びC
成分からなるエポキシ樹脂組成物をD成分である強化繊
維に含浸してなることを特徴とするプリプレグである。
さらに又上記したプリプレグから成型された剛性の低い
FRP製品である。
Further, the following components A, B, C and D: A: a polyepoxy compound having at least two epoxy groups in one molecule B: dicyandiamide C: curing accelerator D: tensile modulus of elasticity 0.4 to 7 tonf / mm 2 and average diameter 11μ
m, a long fiber carbon fiber as an essential component, A, B and C
A prepreg characterized by impregnating a reinforcing fiber as a D component with an epoxy resin composition comprising the components.
Furthermore, it is a low rigidity FRP product molded from the above prepreg.

【0014】以下本発明を詳細に検討する。まず、本発
明においてA成分として用いられるポリエポキシ化合物
は特に制限することなく使用可能であるが、特に例示す
るならばビスフェノールA型エポキシ樹脂、クレゾール
ノボラック型エポキシ樹脂、フェノールノボラック型エ
ポキシ樹脂、ビスフェノールF型エポキシ樹脂、その他
脂環式エポキシ樹脂、ビスフェノールS型エポキシ樹脂
等の内から適宜選択して1種あるいは2種以上を混合し
て用いることができる。ここで市販されているビスフェ
ノールA型エポキシ樹脂としては、エスポキシSA−1
15,エスポキシSA−115CA,エスポキシSA−
127,エスポキシSA−128,エスポキシSA−1
34,エスポキシSA−011,エスポキシSA−01
4,エスポキシSA−017,エスポキシSA−01
9,エスポキシSA−7020(以上新日鐵化学(株)
製)、エピコート828、エピコート834、エピコー
ト1001、エピコート1004(以上油化シェルエポ
キシ(株)製)、アラルダイトGY−250,アラルダイ
トGY−260,アラルダイト6071(以上日本チバ
ガイギー(株)製)等が利用できる。
Hereinafter, the present invention will be described in detail. First, the polyepoxy compound used as the component A in the present invention can be used without any particular limitation, but if specifically exemplified, bisphenol A type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol F One type or a mixture of two or more types can be appropriately selected from a type epoxy resin, other alicyclic epoxy resins, bisphenol S type epoxy resins and the like. As the commercially available bisphenol A type epoxy resin, Espoxy SA-1 is used.
15, Espoxy SA-115CA, Espoxy SA-
127, Espoxy SA-128, Espoxy SA-1
34, Espoxy SA-011, Espoxy SA-01
4, Espoxy SA-017, Espoxy SA-01
9. Espoxy SA-7020 (Nippon Steel Chemical Co., Ltd.)
Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004 (all manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite GY-250, Araldite GY-260, and Araldite 6071 (all manufactured by Nippon Ciba Geigy). it can.

【0015】また市販されているクレゾールノボラック
型エポキシ樹脂としては、エスポキシSCN−701
P,エスポキシSCN−702P,エスポキシSCN−
703P,エスポキシSCN−704P(以上新日鐵化
学(株)製),アラルダイトECN−1273,アラルダ
イトECN−1280(以上日本チバガイギー(株)
製),ESCN−220シリーズ(住友化学工業(株)
製)等が利用できる。また市販されているフェノールノ
ボラック型エポキシ樹脂としては、エスポキシSPN−
638(新日鐵化学(株)製),エピコート152、エピ
コート154(以上油化シェルエポキシ(株)製)、EP
PN−201(日本化薬(株)製)等が利用できる。また
市販されているビスフェノールF型エポキシ樹脂として
は、エピクロン830(大日本インキ化学工業(株)製)
等が利用できる。
A commercially available cresol novolac type epoxy resin is Espoxy SCN-701.
P, Espoxy SCN-702P, Espoxy SCN-
703P, Espoxy SCN-704P (Nippon Steel Chemical Co., Ltd.), Araldite ECN-1273, Araldite ECN-1280 (Nippon Ciba Geigy Co., Ltd.)
ESCN-220 series (Sumitomo Chemical Co., Ltd.)
Manufactured) can be used. As a commercially available phenol novolak type epoxy resin, Espoxy SPN-
638 (manufactured by Nippon Steel Chemical Co., Ltd.), Epicoat 152, Epicoat 154 (manufactured by Yuka Shell Epoxy), EP
PN-201 (manufactured by Nippon Kayaku Co., Ltd.) or the like can be used. As a commercially available bisphenol F type epoxy resin, Epicron 830 (manufactured by Dainippon Ink and Chemicals, Inc.)
Etc. are available.

【0016】次に、B成分として使用される硬化剤とし
ては特に限定するものではないが、ジシアンジアミドが
最適である。この硬化剤の配合量は、A成分100重量
部に対して1〜10重量部にすることが好ましい。ここ
で、この配合量がA成分100重量部に対して1重量部
より少ないと硬化が不十分となり、また、10重量部よ
り多いとFRP製品の強度が低下する。本発明のプリプ
レグはA成分とB成分を必須成分として強化繊維に含浸
したものが有効に使用できる。A,B,C成分には、必
要によって熱可塑性エラストマーやゴム成分を配合した
り、無水シリカ、顔料等を添加することもできる。更に
好ましくは、特にA成分とB成分に対して硬化促進剤で
あるC成分を併用して配合することが望ましい。この場
合の硬化促進剤としては、特にB成分がジシアンジアミ
ドの場合の硬化促進剤となりうる所望の効果を発揮する
もの、即ち、併用することにより140℃以下での温度
での硬化が可能となり、且つシェルライフも20℃で2
ヵ月以上で保つことができるものであることが好まし
い。
The curing agent used as the component B is not particularly limited, but dicyandiamide is optimal. The amount of the curing agent is preferably 1 to 10 parts by weight based on 100 parts by weight of the component A. Here, if the amount is less than 1 part by weight with respect to 100 parts by weight of the component A, curing will be insufficient, and if it is more than 10 parts by weight, the strength of the FRP product will decrease. As the prepreg of the present invention, those obtained by impregnating reinforcing fibers with the A component and the B component as essential components can be used effectively. The A, B, and C components may be blended with a thermoplastic elastomer or a rubber component as necessary, or may be added with anhydrous silica, a pigment, or the like. More preferably, it is particularly desirable to mix the component A and the component B together with the component C which is a curing accelerator. As the curing accelerator in this case, one that exhibits a desired effect that can be a curing accelerator particularly when the B component is dicyandiamide, that is, curing at a temperature of 140 ° C. or less is possible by using together, and Shell life is 2 at 20 ℃
Preferably, it can be kept for more than a month.

【0017】このような硬化促進剤としては、イミタゾ
ール誘導体、例えば、四国化成工業(株)製のキュアゾー
ル2P4MHZ、あるいはイミタゾールのカルボン酸塩
や金属錯体塩等、又は尿素化合物、例えば3−(3、4
−ジクロロフェニル)−1−1−Nジメチル尿素等が優
れた効果を示す。なおA,B成分にC成分を配合する場
合、C成分の配合量はA成分100重量部に対して0.
5〜10重量部にすることが好ましい。ここで、この配
合量がA成分100重量部に対して0.5重量部より少
ないと高い硬化温度が必要となり、また10重量部より
多いとシェルフライフ(保存時間)が短くなる。また、
A,B,C成分には、必要によって熱可塑性エラストマ
ーやゴム成分を配合したり、無水シリカ、顔料等を添加
することもできる。
Examples of such a curing accelerator include an imidazole derivative, for example, Curazole 2P4MHZ manufactured by Shikoku Chemicals Co., Ltd., a carboxylate or metal complex salt of imitazole, or a urea compound such as 3- (3, 4
-Dichlorophenyl) -1-N-dimethylurea and the like show excellent effects. When the component C is mixed with the components A and B, the compounding amount of the component C is 0.1 to 100 parts by weight of the component A.
It is preferable that the amount be 5 to 10 parts by weight. If the amount is less than 0.5 part by weight per 100 parts by weight of the component A, a high curing temperature is required, and if it is more than 10 parts by weight, the shelf life (storage time) becomes short. Also,
The A, B, and C components may be blended with a thermoplastic elastomer or a rubber component as necessary, or may be added with anhydrous silica, a pigment, or the like.

【0018】又、D成分に使用される長繊維炭素繊維と
しては、引張弾性率が0.4〜7tonf/mm2でかつ繊維の
直径が11μm未満である必要がある。なお比重は2.
0未満の長繊維炭素繊維である。ここで引張弾性率が
0.4tonf/mm2未満の炭素繊維は製造が困難であり、
又、7tonf/mm2以上ではFRP製品の剛性の低下にはあ
まり効果を発揮しない。繊維の直径が11μm以上の場
合、目付け(単位面積当たりの炭素繊維の重量)の低い
プリプレグの製造が困難であり、又、例えばゴルフシャ
フトの様な管体を成形する場合、通常金属の芯金の上に
プリプレグのシートを巻き付けさらにその上にポリエチ
レン等のラッピングテープを巻き付け成形を行うが、繊
維の直径が11μm以上の場合、ラッピングテープ上に
樹脂が多くしみ出す。この為、次の研磨工程に移る前に
ラッピングテープをはがす作業が、滲み出した樹脂のた
めに阻害されたり、又、管体の構成や成形条件によりし
み出す樹脂量が変化するため、出来上がるFRP製品の
重量のコントロールが困難になる。比重に関しては通常
の炭素繊維と同等の2.0以下が良くこれ以上になると
軽量化を損なう。
The long-fiber carbon fiber used for the component D must have a tensile modulus of 0.4 to 7 tonf / mm 2 and a fiber diameter of less than 11 μm. The specific gravity is 2.
It is a long-fiber carbon fiber of less than 0. Here, carbon fibers having a tensile modulus of less than 0.4 tonf / mm 2 are difficult to produce,
On the other hand, if it is more than 7 tonf / mm 2 , the effect of reducing the rigidity of the FRP product is not so much exhibited. When the diameter of the fiber is 11 μm or more, it is difficult to produce a prepreg having a low basis weight (weight of carbon fiber per unit area), and when a tubular body such as a golf shaft is formed, a metal core is usually used. A sheet of prepreg is wound on top of this, and a wrapping tape of polyethylene or the like is further wound thereon. When the fiber diameter is 11 μm or more, a large amount of resin exudes on the wrapping tape. For this reason, the operation of peeling the wrapping tape before moving to the next polishing step is hindered due to the exuded resin, or the amount of exuded resin varies depending on the configuration of the tube and the molding conditions, so that the completed FRP It becomes difficult to control the weight of the product. The specific gravity is preferably 2.0 or less, which is equivalent to that of ordinary carbon fibers, and if it is more than 2.0, weight reduction is impaired.

【0019】又引張弾性率が0.4〜7tonf/mm2でかつ
比重が2.0未満の炭素繊維であっても短繊維であれば
一方向のプリプレグを製造することが極めて困難にな
る。又、長繊維炭素繊維としては引張弾性率が0.4〜
7tonf/mm2でかつ繊維の直径が11μm未満でなおかつ
比重が2.0未満の長繊維炭素繊維であればピッチ系炭
素繊維、PAN系炭素繊維、レーヨン系炭素繊維等のい
かなる炭素繊維でも使用できる。ピッチ系炭素繊維とし
ては例えば、エスカイノスNG−P4−10、エスカイ
ノスNG−04C−10、エスカイノスNG−05G−
10(以上新日鐵(株)製)等が好適として例示され、そ
の形態は一方向材、各種織物等の長繊維を何らかの形
状、あるいは形態に加工したものでも全く差し支えな
い。
Even if carbon fibers have a tensile modulus of 0.4 to 7 tonf / mm 2 and a specific gravity of less than 2.0, it is extremely difficult to produce a unidirectional prepreg as long as the fibers are short fibers. Also, as long fiber carbon fiber, the tensile modulus is 0.4 ~
Any carbon fiber such as pitch-based carbon fiber, PAN-based carbon fiber, rayon-based carbon fiber and the like can be used as long as it is 7 tonf / mm 2 and the fiber diameter is less than 11 μm and the specific gravity is less than 2.0. . As the pitch-based carbon fiber, for example, Escainos NG-P4-10, Escainos NG-04C-10, Escainos NG-05G-
10 (above, manufactured by Nippon Steel Corporation) and the like are preferably exemplified, and the form thereof may be a unidirectional material, various fabrics or other long fibers processed into any shape or form.

【0020】プリプレグにする場合、目付量や樹脂含有
率については用途等に応じて適宜設定できるが、目付量
としては例えば25〜300g/m2 にするとよい。目
付量が25g/m2 未満では、薄いプリプレグとなり繊
維を開繊しずらく、また目開きが多くなり均一に繊維が
分散したプリプレグの製造が困難となる。一方、300
g/m2 を越えると、厚いプリプレグとなり繊維に十分
に樹脂が含浸したプリプレグの製造が困難となる。ま
た、樹脂含有率(RC)としては例えば25〜80重量
%にするとよい。25重量%未満では繊維間に樹脂が侵
入しずらく成形品としたとき欠陥が多く疲労特性の劣っ
たものとなる。一方、80重量%を越えるとレジンフロ
ー(樹脂流れ)量が多くなり、ラッピングテープ上に樹
脂が多くしみだし、ラッピングテープを剥がす作業がし
みだした樹脂のために阻害される傾向になる。
When a prepreg is used, the basis weight and the resin content can be appropriately set according to the use and the like, but the basis weight is preferably, for example, 25 to 300 g / m 2 . If the basis weight is less than 25 g / m 2 , the prepreg becomes a thin prepreg, making it difficult to open the fibers, and the openings are increased, making it difficult to produce a prepreg in which the fibers are uniformly dispersed. On the other hand, 300
If it exceeds g / m 2 , it becomes a thick prepreg and it becomes difficult to produce a prepreg in which fibers are sufficiently impregnated with a resin. Further, the resin content (RC) may be, for example, 25 to 80% by weight. If the content is less than 25% by weight, the resin is less likely to penetrate between the fibers, so that the molded article has many defects and is inferior in fatigue characteristics. On the other hand, if it exceeds 80% by weight, the amount of resin flow (resin flow) increases, so that a large amount of resin exudes on the wrapping tape, and the work of removing the wrapping tape tends to be hindered by the exuded resin.

【0021】本発明のプリプレグからFRP製品を成形
するには、芯金に捲着し、常法により樹脂を熱硬化処理
して脱芯するか又はフイラメントワインデイング法や、
オートクレーブ成形法等によって軽量で剛性の低いFR
P製品例えば、ゴルフのシャフトや、釣竿、ベッドの床
板等を成形することができる。なお強化繊維の配向は特
に制限がなく、別途目的により、芯金の軸方向に対して
0〜90°の角度にて適宜複数層積層して配列させ熱硬
化処理した後、適宜表面をベルトサンダーにて研磨する
のが好ましい。
In order to form an FRP product from the prepreg of the present invention, the FRP product is wound around a cored bar, and the resin is heat-cured by a conventional method to remove the core, or a filament winding method,
Lightweight and low rigidity FR by autoclave molding method
P products, for example, golf shafts, fishing rods, bed floor plates, etc. can be formed. The orientation of the reinforcing fibers is not particularly limited, and for a different purpose, after appropriately laminating and arranging a plurality of layers at an angle of 0 to 90 ° with respect to the axial direction of the cored bar and subjecting them to a thermosetting treatment, the surface is appropriately belt-sanded. It is preferable to polish with.

【0022】[0022]

【実施例】以下、実施例により本発明を詳細に説明す
る。 実施例 1 強化繊維としてエスカイノスNG−04C−10(新日
鐵(株)製ピッチ系炭素繊維:比重1.65,引張弾性率
4.5tonf/mm2、繊維径10.3μm)を使用
して、目付け150g/m2,樹脂含有率35wt%の
プリプレグを製造し、このプリプレグを内径5mmの芯
金に3層積層し、130℃で2時間硬化後、表面をベル
トサンダーにて研磨した。得られたパイプ状成形品はボ
イドもなく外観が良いものであった。
The present invention will be described below in detail with reference to examples. Example 1 Using Escainos NG-04C-10 (pitch-based carbon fiber manufactured by Nippon Steel Corporation: specific gravity 1.65, tensile modulus of elasticity 4.5 tonf / mm 2 , fiber diameter 10.3 μm) as a reinforcing fiber. A prepreg having a basis weight of 150 g / m 2 and a resin content of 35 wt% was manufactured, and three layers of the prepreg were laminated on a core metal having an inner diameter of 5 mm. After curing at 130 ° C. for 2 hours, the surface was polished with a belt sander. The obtained pipe-shaped molded article had no voids and had a good appearance.

【0023】比較例1 強化繊維としてケブラー29(東レ・デュポン社製アラ
ミド繊維:比重1.44,引張弾性率4.0tonf/
mm2,繊維径12μm)を使用した以外は実施例1と
同様にパイプ状成形品を作製したが、研磨後、表面にア
ラミド繊維がささくれた状態で現れ、外観の悪いパイプ
となった。
Comparative Example 1 Kevlar 29 (aramid fiber manufactured by Toray DuPont: specific gravity 1.44, tensile modulus 4.0 tonf /
(mm 2 , fiber diameter: 12 μm) except that a pipe-shaped molded product was prepared in the same manner as in Example 1. However, after polishing, aramid fibers appeared on the surface in a cramped state, resulting in a pipe with poor appearance.

【0024】比較例2 強化繊維としてガラス繊維ER1150F−685RG
B(日本電気硝子社製:比重2.54、引張弾性率7.
0tonf/mm2,繊維径13μm)を使用した以外
は実施例1と同様にパイプ状成形品を作製した。得られ
たパイプ状成形品はボイドもなく外観が良いものであっ
たが、実施例と比較して重量の重いパイプとなった。
Comparative Example 2 Glass fiber ER1150F-685RG as a reinforcing fiber
B (manufactured by NEC Corporation: specific gravity 2.54, tensile modulus 7.
A pipe-shaped molded product was produced in the same manner as in Example 1 except that 0 tonf / mm 2 and a fiber diameter of 13 μm) were used. The obtained pipe-shaped molded article had good appearance without voids, but was a pipe heavier than the examples.

【0025】実施例2 強化繊維としてエスカイノスNG−05G−10(新日
鐵(株)製ピッチ系炭素繊維:比重1.60,引張弾性率
4.5tonf/mm2,繊維径10.5μm)を使用
して目付け150g/m2,樹脂含有率35wt%のプ
リプレグを製造した。このプリプレグをAプリプレグと
する。次にトレカT300(東レ社製炭素繊維:比重
1.75,引張弾性率24tonf/mm2 、繊維径7
μm)を使用して目付け150g/m2,樹脂含有率3
5wt%のプリプレグを製造した。このプリプレグをB
プリプレグとする。これらA,Bの2種類のプリプレグ
を使用して内径5mmの芯金に端部から300mmまで
Aプリプレグを5層積層し、300mmから500mm
までBタイププリプレグを使用して5層積層し、さらに
500mmから800mmまでAプリプレグを5層積層
した後に130℃で2時間硬化後、断面を顕微鏡で観察
した。断面にはボイドはなく均一なパイプであった。
Example 2 Escainos NG-05G-10 (pitch-based carbon fiber manufactured by Nippon Steel Corporation: specific gravity 1.60, tensile modulus 4.5 tonf / mm 2 , fiber diameter 10.5 μm) was used as a reinforcing fiber. A prepreg having a basis weight of 150 g / m 2 and a resin content of 35 wt% was produced. This prepreg is referred to as A prepreg. Next, Torayca T300 (Toray carbon fiber: specific gravity 1.75, tensile modulus of elasticity 24 tonf / mm 2 , fiber diameter 7
150 g / m 2 , resin content 3
A 5 wt% prepreg was produced. This prepreg is B
Prepreg. Using these two types of prepregs A and B, five layers of A prepregs are laminated on a core metal having an inner diameter of 5 mm from the end to 300 mm, and from 300 mm to 500 mm
Five layers were laminated using a B-type prepreg, and five layers of A prepreg were further laminated from 500 mm to 800 mm. After curing at 130 ° C. for 2 hours, the cross section was observed with a microscope. The cross section was a uniform pipe without voids.

【0026】比較例3 テクミロン(三井石油化学工業社製 ポリエチレン繊
維:比重0.96,引張弾性率6tonf/mm2,繊
維径38μm)を使用して目付け150g/m2,樹脂
含有率35wt%のプリプレグを製造した。このプリプ
レグをCプリプレグとする。実施例2のAプリプレグの
かわりにCプリプレグを使用した以外は実施例2と同様
にパイプを製造し断面を観察した。このパイプはAプリ
プレグとCプリプレグの界面で厚みに差があり、またボ
イドが多く観察された。
Comparative Example 3 Using Techmilon (polyethylene fiber manufactured by Mitsui Petrochemical Industries, Ltd .: specific gravity 0.96, tensile modulus 6 tonf / mm 2 , fiber diameter 38 μm), a basis weight of 150 g / m 2 and a resin content of 35 wt% A prepreg was manufactured. This prepreg is referred to as C prepreg. A pipe was manufactured and the cross section was observed in the same manner as in Example 2, except that C prepreg was used instead of A prepreg of Example 2. This pipe had a difference in thickness at the interface between the A prepreg and the C prepreg, and many voids were observed.

【0027】実施例3 強化繊維としてエスカイノスNG−05G−10(新日
鐵(株)製 ピッチ系炭素繊維:比重1.60,引張弾性
率4.5tonf/mm2,繊維径10.5μm)を使
用して目付け30g/m2,樹脂含有率37wt%のプ
リプレグを製造した。このプリプレグをDプリプレグと
する。このDプリプレグは目開き(炭素繊維ストランド
間の空隙)は無く、又平滑性に優れた品質の高いもので
あった。このDプリプレグを使用し、直径2mmの芯金
に芯金の長さ方向と炭素繊維の方向を平行にして幅80
0mmで7層積層した。次にポリエチレン製のラッピン
グテープを3mmの間隔で巻き付けた後に、電気炉で1
30℃で2時間の成形を行った。成形後、ラッピングテ
ープ上に樹脂は殆どしみだしておらず、ラッピングテー
プの除去は容易なものであった。又、以下の(1)式で
定義するレジンフロー量を測定したところ、1%であっ
た。
Example 3 Escainos NG-05G-10 (pitch-based carbon fiber manufactured by Nippon Steel Corporation: specific gravity 1.60, tensile modulus 4.5 tonf / mm 2 , fiber diameter 10.5 μm) was used as a reinforcing fiber. A prepreg having a basis weight of 30 g / m 2 and a resin content of 37 wt% was produced. This prepreg is referred to as D prepreg. This D prepreg had no openings (voids between carbon fiber strands) and had high quality with excellent smoothness. Using this D prepreg, the length of the core metal and the direction of the carbon fiber are parallel to a core metal having a diameter of 2 mm, and a width of 80 mm.
Seven layers were stacked at 0 mm. Next, after wrapping a wrapping tape made of polyethylene at an interval of 3 mm, 1
Molding was performed at 30 ° C. for 2 hours. After molding, the resin hardly oozed on the wrapping tape, and the wrapping tape was easily removed. When the resin flow amount defined by the following equation (1) was measured, it was 1%.

【数1】 (Equation 1)

【0028】比較例4 強化繊維としてエスカイノス NG−05G(新日鐵
(株)製 ピッチ系炭素繊維:比重1.60,引張弾性率
4.5tonf/mm2,繊維径13.0μm)を使用
した以外は実施例3と同様にしてプリプレグを製造し
た。このプリプレグをEプリプレグとする。このEプリ
プレグは幅約2mm,長さ約10−30mm程度の目開
き(炭素繊維ストランド間の空隙)が1mの長さの間に
2−3個存在し、又表面の平滑性が悪い品質の低いもの
であった。このEプリプレグを使用して実施例3と同様
に管体を成形したところ、ラッピングテープ上に多くの
樹脂がしみだしてき、ラッピングテープの除去は極めて
困難なものであった。又、(1)式から求めたレジンフ
ロー量は4.5%であった。
Comparative Example 4 Escainos NG-05G (Nippon Steel) as a reinforcing fiber
A prepreg was produced in the same manner as in Example 3 except that pitch-based carbon fiber manufactured by Co., Ltd .: specific gravity 1.60, tensile modulus of elasticity 4.5 tonf / mm 2 , fiber diameter 13.0 μm) was used. This prepreg is referred to as E prepreg. This E prepreg has a number of openings (gap between carbon fiber strands) of about 2 mm in width and about 10-30 mm in length in a length of 1 m, and has a quality of poor surface smoothness. It was low. When a tube was formed using this E prepreg in the same manner as in Example 3, a large amount of resin exuded onto the wrapping tape, and it was extremely difficult to remove the wrapping tape. Further, the resin flow amount obtained from the equation (1) was 4.5%.

【0029】[0029]

【発明の効果】本発明のプリプレグは、軽量で剛性が低
いFRP製品用としての成形加工性に優れているため設
計の自由度が高い。また、このプリプレグを成形するこ
とにより得られる繊維強化プラスチックス(以下FRP
と略記)は、軽量で剛性が低くボイド等もない外観の良
いものが得られる。また一部が剛性の低いFRP製品用
にも好適である。従って最近要求されるようになってき
た軽量で剛性の低いFRP製品例えば、ゴルフのシャフ
トや、釣竿、ベッドの床板等の成形に好適である。
As described above, the prepreg of the present invention has a high degree of freedom in design because it is excellent in molding processability for FRP products which are lightweight and have low rigidity. Further, fiber reinforced plastics (hereinafter referred to as FRP) obtained by molding this prepreg.
Abbreviated) can be obtained which is light in weight, has low rigidity and good appearance without voids or the like. It is also suitable for FRP products with low rigidity. Therefore, it is suitable for forming a lightweight and low-rigidity FRP product that has recently been required, for example, a golf shaft, a fishing rod, a bed plate of a bed, and the like.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI B29K 105:08 307:04 C08L 63:00 (56)参考文献 特開 平8−12860(JP,A) 特開 平7−228716(JP,A) 特開 平7−41564(JP,A) (58)調査した分野(Int.Cl.6,DB名) C08J 5/24 C08J 5/04 ────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. 6 Identification symbol FI B29K 105: 08 307: 04 C08L 63:00 (56) References JP-A-8-12860 (JP, A) JP-A-7- 228716 (JP, A) JP-A-7-41564 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C08J 5/24 C08J 5/04

Claims (5)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 下記A、B及びD成分 A;一分子中に少なくとも二個以上のエポキシ基を持つ
ポリエポキシ化合物 B;硬化剤 D;引張弾性率0.4〜7tonf/mm2かつ平均直径11μ
m以下の長繊維炭素繊維を必須成分とし、A及びB成分
を含有するエポキシ樹脂組成物をD成分である強化繊維
に含浸してなることを特徴とするプリプレグ。
1. Components A, B and D shown below: A; a polyepoxy compound having at least two epoxy groups in one molecule B; a curing agent D; a tensile modulus of 0.4 to 7 tonf / mm 2 and an average diameter 11μ
A prepreg characterized by comprising a long fiber carbon fiber of m or less as an essential component and impregnating a reinforcing fiber as a D component with an epoxy resin composition containing A and B components.
【請求項2】 下記A、B、C及びD成分 A;一分子中に少なくとも二個以上のエポキシ基を持つ
ポリエポキシ化合物 B;ジシアンジアミド C;硬化促進剤 D;引張弾性率0.4〜7tonf/mm2かつ平均直径11μ
m以下の長繊維炭素繊維を必須成分とし、A、B及びC
成分からなるエポキシ樹脂組成物をD成分である強化繊
維に含浸してなることを特徴とするプリプレグ:
2. The following components A, B, C and D: A; a polyepoxy compound having at least two epoxy groups in one molecule B; dicyandiamide C; a curing accelerator D; a tensile modulus of elasticity of 0.4 to 7 tonf / mm 2 and an average diameter of 11μ
m, a long fiber carbon fiber as an essential component, A, B and C
A prepreg characterized by impregnating an epoxy resin composition comprising a component into a reinforcing fiber as a component D:
【請求項3】 D成分の目付量が25〜300g/m2
であり、エポキシ樹脂組成物の含有率(RC)が25〜
80重量%である請求項1又は請求項2記載のプリプレ
グ。
3. The basis weight of the D component is 25 to 300 g / m 2.
And the content (RC) of the epoxy resin composition is 25 to
The prepreg according to claim 1 or 2, which is 80% by weight.
【請求項4】 D成分の長繊維炭素繊維がピッチ系炭素
繊維である請求項1〜請求項4のいずれかに記載のプリ
プレグ。
4. The prepreg according to claim 1, wherein the long fiber carbon fibers of the D component are pitch-based carbon fibers.
【請求項5】 請求項1又は請求項2記載のプリプレグ
で少なくとも一部が成形された剛性の低いFRP製品。
5. A low-rigidity FRP product formed at least in part from the prepreg according to claim 1.
JP2699295A 1995-02-15 1995-02-15 Prepreg and its FRP products Expired - Lifetime JP2989506B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2699295A JP2989506B2 (en) 1995-02-15 1995-02-15 Prepreg and its FRP products

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2699295A JP2989506B2 (en) 1995-02-15 1995-02-15 Prepreg and its FRP products

Publications (2)

Publication Number Publication Date
JPH08217896A JPH08217896A (en) 1996-08-27
JP2989506B2 true JP2989506B2 (en) 1999-12-13

Family

ID=12208664

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2699295A Expired - Lifetime JP2989506B2 (en) 1995-02-15 1995-02-15 Prepreg and its FRP products

Country Status (1)

Country Link
JP (1) JP2989506B2 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6273830B1 (en) 1996-04-19 2001-08-14 Nippon Mitsubishi Oil Corporation Tapered hollow shaft
CN102139545B (en) * 2003-10-22 2014-08-27 Ctc电缆公司 Aluminum conductor composite core reinforced cable and method of manufacturing the same
US20080286522A1 (en) * 2006-12-15 2008-11-20 Subhotosh Khan Honeycomb having a low coefficient of thermal expansion and articles made from same
CN105062003A (en) * 2015-08-17 2015-11-18 陈志� Light insulating fishing rod

Also Published As

Publication number Publication date
JPH08217896A (en) 1996-08-27

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