JPH0820708A - Epoxy resin composition and prepreg prepared therefrom - Google Patents
Epoxy resin composition and prepreg prepared therefromInfo
- Publication number
- JPH0820708A JPH0820708A JP15478794A JP15478794A JPH0820708A JP H0820708 A JPH0820708 A JP H0820708A JP 15478794 A JP15478794 A JP 15478794A JP 15478794 A JP15478794 A JP 15478794A JP H0820708 A JPH0820708 A JP H0820708A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- prepreg
- curing agent
- resin composition
- resin
- 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.)
- Pending
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明はプリプレグの適度なタッ
ク性(粘着性)、ドレープ性(柔軟性)等の取扱い作業
性と室温での保存安定性に優れ、80℃付近の比較的低
温で成形可能であり、また成形時のレジンフローが少な
く、特に釣竿やゴルフシャフト等の繊維強化樹脂製の管
状成形体の成形時に炉落ちがなく、これら成形体研磨表
面にキズ等の欠陥がない、優れた複合材料特性を有する
繊維強化複合材に適したエポキシ樹脂組成物に関する。BACKGROUND OF THE INVENTION The present invention is excellent in handling workability such as moderate tackiness (adhesiveness) and drapeability (flexibility) of prepreg and storage stability at room temperature, and can be used at a relatively low temperature around 80 ° C. Moldable, less resin flow at the time of molding, especially when molding tubular moldings made of fiber reinforced resin such as fishing rods and golf shafts, there is no furnace fall, and there are no defects such as scratches on the polished surface of these moldings. The present invention relates to an epoxy resin composition suitable for a fiber-reinforced composite material having excellent composite material properties.
【0002】[0002]
【従来の技術】炭素繊維等の繊維強化複合材料は、軽量
であって高強度、高弾性率を有し、樹脂との複合体、い
わゆるプリプレグの形で、例えば釣竿、ゴルフクラブの
シャフト、テニスラケット等のスポーツ・レジャー分
野、板バネやハニカム構造材等の工業材料、さらには自
動車関連、航空機材料、船舶等の構造材料、電子材料、
土木建築材料等さまざまな用途に広く用いられている。BACKGROUND OF THE INVENTION Fiber-reinforced composite materials such as carbon fibers are lightweight, have high strength and high elastic modulus, and are in the form of composites with resins, so-called prepregs, such as fishing rods, golf club shafts, and tennis. Sports / leisure fields such as rackets, industrial materials such as leaf springs and honeycomb structure materials, as well as automobile-related, aircraft materials, structural materials such as ships, electronic materials,
Widely used for various purposes such as civil engineering and building materials.
【0003】このような繊維強化複合材料用プリプレグ
に要求される特性としては、適度な取扱作業性、室温に
おける保存安定性、硬化物の機械的特性に優れる事はも
とより、近年船舶や車輛のような大型構造材の成形、ま
た木型や樹脂型を用いた成形等に関して、より低温短時
間の硬化要求が望まれており、成形サイクルの短縮化、
エネルギーコストの低減要求が高まっている。The properties required for such a prepreg for a fiber-reinforced composite material include not only excellent handling workability, storage stability at room temperature, and mechanical properties of a cured product, but also the properties of a ship or vehicle in recent years. For molding large-scale structural materials, and molding using wooden molds and resin molds, there is a demand for curing at a lower temperature and for a shorter time, which shortens the molding cycle,
There is an increasing demand to reduce energy costs.
【0004】ところで従来この様な繊維強化複合材料用
プリプレグのマトリックス樹脂としては、エポキシ樹脂
を用いたもの(特開昭62−127317号公報、特開
平2−41314号公報)、またこれらのマトリックス
樹脂に、補強単繊維径の10倍以下の粒径である充填
剤、例えば黒鉛粉末、カーボンブラック、アルミニウム
粉末、シリカパウダー等を添加し、プリプレグ成形時の
マトリックス樹脂の流動性を低下したもの(特開昭59
−227931号公報)等がプリプレグの製造に用いら
れている。By the way, as a matrix resin for such a prepreg for a fiber-reinforced composite material, an epoxy resin is used (Japanese Patent Laid-Open Nos. 62-127317 and 2-41314), and these matrix resins. A filler having a particle diameter of 10 times or less the diameter of the reinforcing single fiber, for example, graphite powder, carbon black, aluminum powder, silica powder, etc., is added to reduce the fluidity of the matrix resin during prepreg molding ( Kaisho 59
No. 227931) is used for manufacturing prepreg.
【0005】また低温硬化用プリプレグとしては、特開
平5−9262号公報、特開平6−9802号公報に、
100℃以下の比較的低温で硬化する潜在性硬化剤を用
いたプリプレグについて提案されている。これらのマト
リックス樹脂は、従来のものと比較してプリプレグの製
造時、保存安定性を低下させないために、より低温で強
化繊維に含浸する必要があり、そのため樹脂粘度は低め
に設定する必要がある。Further, as low-temperature curing prepregs, there are disclosed in Japanese Unexamined Patent Publications No. 5-9262 and No. 6-9802.
A prepreg using a latent curing agent that cures at a relatively low temperature of 100 ° C. or lower has been proposed. These matrix resins need to be impregnated into the reinforcing fibers at a lower temperature in order to prevent deterioration in storage stability during the production of the prepreg as compared with the conventional ones, and therefore the resin viscosity needs to be set to be low. .
【0006】特に釣竿やゴルフシャフト等の管状の繊維
強化複合材料は、炭素繊維やガラス繊維を一方向に引き
揃えたシート状のプリプレグまたは上記強化繊維の織物
にマトリックス樹脂を含浸したプリプレグを離型剤を塗
布したテーパー付マンドレルに長手方向に対して、所望
の設計に応じた方向に巻付け、さらにその上に熱収縮性
テープをテープワインダー等を用いて少しずつオーバー
ラップさせながら螺旋状に巻付け、次いで加熱炉に入
れ、熱収縮性テープによる締付力を付与しながらマトリ
ックス樹脂を硬化し、加熱炉から取出して冷却後テープ
を取り除き、脱芯機等によりマンドレルを引抜いて成形
している。しかし従来のプリプレグでは、成形時にマン
ドレルの大径側から小径側に向かってプリプレグが移動
する、いわゆる炉落ちが発生するという欠点を生じてい
た。これは、加熱によってマトリックス樹脂が低粘度化
し流動性を増すため、このような状態で熱収縮性テープ
による締め付け力が加わると、マンドレルがテーパーを
有しているため、大径側から小径側に分力が生じ、この
方向にプリプレグが移動する、いわゆる炉落ちが発生す
る。この炉落ちが発生すると、マトリックス樹脂や強化
繊維に分布のむらができ、所望の複合材料物性が得られ
ないばかりか、成形品の欠陥の原因または小径部の反り
発生原因ともなる。In particular, for tubular fiber-reinforced composite materials such as fishing rods and golf shafts, a sheet-shaped prepreg in which carbon fibers or glass fibers are aligned in one direction or a prepreg obtained by impregnating a woven fabric of the above-mentioned reinforcing fibers with a matrix resin is released. Wrap the taped mandrel coated with the agent in the longitudinal direction in the direction according to the desired design, and then wind the heat-shrinkable tape in a spiral shape using a tape winder etc. while gradually overlapping it. Then, put it in a heating furnace, harden the matrix resin while applying tightening force with heat shrinkable tape, remove from the heating furnace and remove the tape after cooling, pull out the mandrel with a core removing machine etc. . However, the conventional prepreg has a drawback that the prepreg moves from the large diameter side of the mandrel toward the small diameter side during molding, that is, so-called furnace drop occurs. This is because heating causes the matrix resin to have low viscosity and to increase fluidity, so when the tightening force of the heat-shrinkable tape is applied in such a state, the mandrel has a taper, and the mandrel has a taper from the large diameter side to the small diameter side. A component force is generated and a so-called furnace drop occurs in which the prepreg moves in this direction. When this furnace drop occurs, the distribution of the matrix resin and the reinforcing fibers becomes uneven, and the desired physical properties of the composite material cannot be obtained, and it also causes defects in the molded product or warpage of the small diameter portion.
【0007】一方、特開昭57−22636号公報に、
マンドレルへのプリプレグ巻き付けに先立って、糸また
は熱硬化性樹脂を含浸した糸をマンドレルの長手方向に
螺旋状に巻付け、その摩擦により炉落ちを防止する方法
が提案されている。しかし、この方法では、炉落ち防止
効果が十分でないばかりか、糸が成形品中に残存し特性
上好ましくない。また特開昭59−159315号公報
には、マンドレルにプリプレグを捲回するのに先立っ
て、プリプレグ用マトリックス樹脂に対して、130℃
におけるゲルタイムが前記樹脂の80%以下の熱硬化樹
脂をマンドレルに塗布することにより、炉落ちを防止す
る方法が提案されている。しかしこの方法では、B−ス
テージ化によりゲルタイムを調整した下塗用の樹脂が必
要であり、成形に先立ち、この下塗り樹脂の塗布工程、
風乾が必要で、著しく生産性を低下する。更にこれらの
プリプレグは、100℃以上の硬化温度が必要である。On the other hand, Japanese Unexamined Patent Publication No. 57-22636 discloses that
Prior to winding the prepreg around the mandrel, a method has been proposed in which a thread or a thread impregnated with a thermosetting resin is spirally wound in the longitudinal direction of the mandrel and the friction thereof prevents the furnace from falling. However, in this method, not only the effect of preventing the furnace from falling is not sufficient, but also the yarn remains in the molded product, which is not preferable in terms of characteristics. Further, in Japanese Patent Laid-Open No. 59-159315, a temperature of 130 ° C. is applied to a matrix resin for prepreg before winding the prepreg around a mandrel.
There is proposed a method of preventing the furnace from falling by applying a thermosetting resin having a gel time of 80% or less of the above resin to the mandrel. However, this method requires a resin for undercoating whose gel time is adjusted by B-stage formation, and prior to molding, the step of applying this undercoating resin,
Air-drying is required, which significantly reduces productivity. Furthermore, these prepregs require a curing temperature of 100 ° C. or higher.
【0008】またプリプレグの作業時の取扱性(タッ
ク、ドレープ性)に関しては、シャフト捲回時の生産性
のみならず、成形品表面の欠陥(キズ等)の原因ともな
るため適度な特性が要求される。タック性が強すぎると
捲回時にエアーを巻き込みやすく、低すぎるとプリプレ
グの張り合わせ等の作業性が低下する。またドレープ性
が不十分の場合にはプリプレグ捲回時に巻終り部分にハ
ネを生じ、特に高弾性率の炭素繊維では折れの原因とも
なる。しかるに、これらの因子がシャフト成形後の研
磨、塗装時にキズ等の欠陥として表面に現れ、不良品の
発生、物性の低下の原因になっており、著しく歩留まり
を低下させていた。Regarding the handling property (tack and drape property) of the prepreg at the time of working, not only the productivity at the time of winding the shaft but also a defect (scratch etc.) on the surface of the molded product is required, so that appropriate characteristics are required. To be done. If the tackiness is too strong, air is likely to be entrained at the time of winding, and if it is too low, workability such as laminating the prepreg deteriorates. In addition, when the drape property is insufficient, the prepreg is wound at the end portion of the winding, and particularly carbon fibers having a high elastic modulus may be broken. However, these factors appear on the surface as defects such as scratches at the time of polishing and coating after molding the shaft, causing defective products and deteriorating the physical properties, resulting in a significant reduction in yield.
【0009】このように従来のマトリックス樹脂組成物
を用いたプリプレグでは、適度な作業性と優れた複合材
料特性を有し、室温での保存安定性が良好であり、10
0℃以下の成形で十分硬化して、成形時の炉落ちがな
く、成形品の研磨、塗装面に欠陥のないプリプレグを提
供する事は極めて困難であった。As described above, the prepreg using the conventional matrix resin composition has appropriate workability and excellent composite material properties, and has good storage stability at room temperature.
It was extremely difficult to provide a prepreg that is sufficiently cured by molding at 0 ° C. or lower, does not fall in the furnace during molding, and has no defects on the polished or coated surface of the molded product.
【0010】[0010]
【発明が解決しようとする課題】本発明の目的は、従来
の方法の上記欠点を解決し、前処理工程を行うことなく
成形時の炉落ちを防止することができ、複合材料特性を
低下することなく、100℃以下の比較的低温で成形が
可能であり、所望の特性を有する繊維強化複合材料成形
品を得ることができる。また、本発明のエポキシ樹脂組
成物を用いたプリプレグは通常の捲回温度に於て、適度
な捲回作業性を有し、また成形時のレジンフローを自由
にコントロールできるため、研磨後の成形品表面に欠陥
(キズ等)のない優れた成形体を提供するものである。SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of the conventional method, prevent the furnace from falling during molding without performing a pretreatment step, and deteriorate the composite material properties. It is possible to carry out molding at a relatively low temperature of 100 ° C. or less without giving rise to a fiber-reinforced composite material molded product having desired properties. Further, the prepreg using the epoxy resin composition of the present invention has an appropriate winding workability at a normal winding temperature, and since the resin flow during molding can be freely controlled, it can be molded after polishing. The object of the present invention is to provide an excellent molded product having no defects (such as scratches) on the product surface.
【0011】[0011]
【課題を解決するための手段】すなわち本発明は、下記
(A)、(B)および(C)成分 (A)エポキシ樹脂100重量部に対し (B)低温活性潜在性硬化剤3〜60重量部及び (C)アスペクト比が3以上、500以下のウィスカー
0.05〜30重量部 を必須成分とするエポキシ樹脂組成物とこれを用いたプ
リプレグに存する。Means for Solving the Problems That is, the present invention relates to the following components (A), (B) and (C) (A) 100 parts by weight of an epoxy resin (B) 3 to 60 parts by weight of a low temperature active latent curing agent. Parts and (C) 0.05 to 30 parts by weight of whiskers having an aspect ratio of 3 or more and 500 or less as an essential component, and a prepreg using the same.
【0012】以下本発明をより詳細に説明する。本発明
に用いられる(A)成分であるエポキシ樹脂は特に限定
されるものではなく、ビスフェノールA型エポキシ樹
脂、他のグリシジルエーテル型エポキシ樹脂、例えば、
ビスフェノールF型エポキシ樹脂、ビスフェノールS型
エポキシ樹脂、またフェノールノボラック型エポキシ樹
脂、クレゾールノボラック型エポキシ樹脂、グリシジル
アミン型エポキシ樹脂、ナフタレン型エポキシ樹脂、臭
素化ビスフェノールA型エポキシ樹脂、グリシジルエス
テル型エポキシ樹脂、環式脂肪族エポキシ樹脂、複素環
式エポキシ樹脂等が挙げられる。また所望に応じて、ウ
レタン変性エポキシ樹脂、ゴム変性エポキシ樹脂、アル
キド変性エポキシ樹脂等を用いても良い。これらのうち
取扱い性、経済性、複合材料物性のバランスよりビスフ
ェノールA型エポキシ樹脂、およびノボラック型エポキ
シ樹脂が好ましいが、必要特性に応じてこれらの2種以
上を適宜混合して用いることができる。The present invention will be described in more detail below. The epoxy resin which is the component (A) used in the present invention is not particularly limited, and includes a bisphenol A type epoxy resin and other glycidyl ether type epoxy resins, for example,
Bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl amine type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, glycidyl ester type epoxy resin, Examples thereof include cycloaliphatic epoxy resins and heterocyclic epoxy resins. If desired, urethane-modified epoxy resin, rubber-modified epoxy resin, alkyd-modified epoxy resin, etc. may be used. Among these, bisphenol A type epoxy resin and novolac type epoxy resin are preferable from the viewpoint of balance of handling property, economical efficiency, and physical properties of composite material, but two or more kinds of these can be appropriately mixed and used according to required characteristics.
【0013】(B)成分の低温活性潜在性系硬化剤とし
ては、50℃以上で活性化するものが用いられ、好まし
くは80℃付近で活性化する熱硬化性潜在性硬化剤であ
る。例えば熱溶融により活性化するアミンアダクト型の
潜在性硬化剤(アミキュア:味の素(株)社製商標)、
隔壁破壊型のマイクロカプセル型潜在性硬化剤(ノバキ
ュア:旭化成工業(株)社製商標)等があり、これらの
潜在性硬化剤は、50℃付近では保存安定性が良好であ
り、80℃付近より急速活性化しエポキシ樹脂を硬化さ
せる。これらの潜在性硬化剤の添加量は、(A)成分で
あるエポキシ樹脂100重量部に対し3〜60重量部が
用いられる。3重量部より少ないと硬化が遅く十分な特
性が得られず、100重量部を超えると、室温付近での
保存安定性の低下や硬化物物性の低下が顕著であり好ま
しくない。またこれらの潜在性硬化剤は、単独で用いる
方が80℃付近での硬化反応性は良好であるが、反応性
または保存安定性の適度なコントロール等の目的より、
特性を低下させない程度の尿素化合物、グアニジン化合
物、多価カルボン酸ポリヒドラジド化合物、アミンイミ
ド、ジアミノマレオニトリル、グアナミン類、フェノー
ル樹脂、メラミン樹脂、ユリア樹脂等を所望に応じて適
宜混合して用いることができる。As the low temperature active latent curing agent as the component (B), those which are activated at 50 ° C. or higher are used, and preferably thermosetting latent curing agents which are activated at around 80 ° C. For example, an amine adduct-type latent curing agent that is activated by heat melting (Amicure: trademark of Ajinomoto Co., Inc.),
There are partition wall breaking type microcapsule type latent curing agents (Novacure: trademark of Asahi Chemical Industry Co., Ltd.) and the like. These latent curing agents have good storage stability at around 50 ° C and around 80 ° C. It activates more rapidly and cures the epoxy resin. The addition amount of these latent curing agents is 3 to 60 parts by weight with respect to 100 parts by weight of the epoxy resin which is the component (A). If it is less than 3 parts by weight, the curing will be slow and sufficient properties cannot be obtained, and if it exceeds 100 parts by weight, the storage stability at room temperature and the physical properties of the cured product will be significantly deteriorated, which is not preferable. Further, these latent curing agents have better curing reactivity at around 80 ° C. when used alone, but for the purpose of appropriate control of reactivity or storage stability,
Urea compounds, guanidine compounds, polyhydric carboxylic acid polyhydrazide compounds, amine imides, diaminomaleonitriles, guanamines, phenol resins, melamine resins, urea resins, etc. may be appropriately mixed and used as long as the characteristics are not deteriorated. it can.
【0014】(C)成分であるウィスカーとしては、ア
スペクト比(繊維の長さ/繊維の直径)が3以上、50
0以下、好ましくは450以下のものが用いられる。ア
スペクト比が3より小さいと、成形時のレジンフローが
十分に低くならず、またアスペクト比が500を超える
と強化繊維への含浸性またはプリプレグの作業性、成形
性に悪影響をもたらす。これらのウィスカーは特に限定
されるものではなく、例えばホウ酸アルミニウム、炭酸
カルシウム、炭酸ケイ素、窒化ケイ素、チタン酸カリウ
ム、塩基性硫酸マグネシウム、酸化亜鉛、グラファイ
ト、マグネシア、硫酸カルシウム、ホウ酸マグネシウ
ム、二ホウ化チタン、α−アルミナ、クリソタイル等の
一種または二種以上が適宜用いられる。これらのうち特
にホウ酸アルミニウム、炭酸カルシウム、炭化ケイ素ウ
ィスカーが特性、経済性の点で優れる。これらウィスカ
ーの添加量は、(A)成分100重量部に対し、0.0
5〜30重量部、好ましくは0.5〜15重量部が用い
られる。0.05重量部より少ないと成形時の十分なフ
ローの低下はなく、30重量部を超えると樹脂の粘度が
上昇し、プリプレグ化工程での繊維への含浸性が低下し
やすく好ましくない。The whiskers as the component (C) have an aspect ratio (fiber length / fiber diameter) of 3 or more, 50 or more.
Those of 0 or less, preferably 450 or less are used. If the aspect ratio is less than 3, the resin flow at the time of molding will not be sufficiently low, and if the aspect ratio exceeds 500, the impregnability into reinforcing fibers or the workability and moldability of prepreg will be adversely affected. These whiskers are not particularly limited, and examples thereof include aluminum borate, calcium carbonate, silicon carbonate, silicon nitride, potassium titanate, basic magnesium sulfate, zinc oxide, graphite, magnesia, calcium sulfate, magnesium borate, and diborate. One or more of titanium boride, α-alumina, chrysotile, etc. are appropriately used. Of these, aluminum borate, calcium carbonate, and silicon carbide whiskers are particularly excellent in properties and economical efficiency. The addition amount of these whiskers is 0.0 with respect to 100 parts by weight of the component (A).
5 to 30 parts by weight, preferably 0.5 to 15 parts by weight are used. If the amount is less than 0.05 parts by weight, the flow during molding will not be sufficiently reduced, and if it exceeds 30 parts by weight, the viscosity of the resin will increase and the impregnability into the fiber in the prepreg-forming step tends to deteriorate, such being undesirable.
【0015】これら上記成分以外に、所望によって強化
繊維への含浸性を低下させない程度または反応性、耐熱
性、貯蔵安定性等の低下をさせない程度の熱可塑性樹
脂、エポキシド反応性希釈剤を添加しても良い。熱可塑
性樹脂の例としては、フェノキシ樹脂、ポリビニルブチ
ラール、ポリビニルホルマール、ポリビニルフェニルア
セタール等のアセタール樹脂、ポリエーテルスルホン、
ポリスルホン、ポリエーテルイミド、ポリアリレート等
が挙げられ、また反応性希釈剤の例としては、フェニル
グリシジルエーテル、ブチルグリシジルエーテル、アル
キルグリシジルエーテル、スチレンオキサイド、オクチ
レンオキサイド及びこれらの混合物等が挙げられる。こ
の他、シラン、チタネート化合物等のカップリング剤、
高級脂肪酸およびワックス等の離型剤、ハロゲン、リン
化合物等の難燃性付与剤、消泡剤、着色剤、低温発泡剤
等の添加剤も必要に応じ用いることができる。In addition to the above components, if desired, a thermoplastic resin and an epoxide-reactive diluent are added to such an extent that the impregnability into the reinforcing fiber is not lowered or the reactivity, heat resistance, storage stability and the like are not lowered. May be. Examples of thermoplastic resin include phenoxy resin, polyvinyl butyral, polyvinyl formal, acetal resin such as polyvinyl phenyl acetal, polyether sulfone,
Examples thereof include polysulfone, polyetherimide, polyarylate and the like, and examples of the reactive diluent include phenyl glycidyl ether, butyl glycidyl ether, alkyl glycidyl ether, styrene oxide, octylene oxide and mixtures thereof. In addition, coupling agents such as silane and titanate compounds,
Additives such as releasing agents such as higher fatty acids and waxes, flame retardants such as halogens and phosphorus compounds, defoamers, colorants, low-temperature foaming agents and the like can be used if necessary.
【0016】またこれらプリプレグの製造に用いられる
強化繊維としては、炭素繊維、ガラス繊維、アラミド繊
維、ポリエステル繊維、炭化ケイ素繊維、ボロン繊維、
アルミナ繊維、ポリエチレン繊維等が挙げられ、これら
の一種もしくは二種以上を適宜使用する。そしてこのう
ち得られる硬化後の成形体の強度や導電率の点で炭素繊
維が特に好ましい。The reinforcing fibers used in the production of these prepregs include carbon fibers, glass fibers, aramid fibers, polyester fibers, silicon carbide fibers, boron fibers,
Alumina fibers, polyethylene fibers, etc. may be mentioned, and one kind or two or more kinds of them may be appropriately used. Of these, carbon fiber is particularly preferable in terms of strength and conductivity of the obtained molded product after curing.
【0017】プリプレグを製造するには、一般のプリプ
レグ製造方法が適用でき、補強基材に対し例えばホット
メルト法により直接あるいはフィルム法で含浸するか、
溶媒含浸法により直接あるいはフィルム化後含浸のいず
れかを用いれば良いが、溶媒含浸法では溶剤留去工程が
必要であり、また樹脂組成物の安定性を低下させること
があり、あまり好ましくない。In order to manufacture the prepreg, a general prepreg manufacturing method can be applied, and the reinforcing base material is impregnated directly or by the film method, for example.
Either the direct impregnation method or the post-film-forming impregnation method may be used, but the solvent impregnation method requires a solvent distillation step and may reduce the stability of the resin composition, which is not preferable.
【0018】[0018]
【実施例】以下に本発明を実施例によりさらに詳しく説
明するが、本発明はこれらの実施例によって限定される
ものではない。尚、実施例中に用いた化合物の略号、お
よび試験法は以下の通りである。 <原料> 「E828」:ビスフェノールA型エポキシ樹脂(油化
シェル社製) 「E1001」:ビスフェノールA型エポキシ樹脂(油
化シェル社製) 「PN−23」、「MY−24」:アミンアダクト型潜
在性硬化剤(味の素社製) 「HX−3722」:マイクロカプセル型潜在性硬化剤
(旭化成社製)〔E828/硬化剤=2/3重量部マス
ターバッチ〕 DICY:ジシアンジアミド(油化シェル社製) DCMU:3−(3,4−ジクロロフェニル)−1,1
−Nジメチル尿素(保土ヶ谷化学社製) 「アルボレックスYS2」、「YS3」:ホウ酸アルミ
ニウムウィスカー(四国化成工業(株)社製)<アスペ
クト比=10〜60> 「ウィスカル」:炭酸カルシウムウィスカー(四国化成
工業(株)社製)<アスペクト比=20〜60> 「R202」:微粉シリカ、アエロジルR202 (日本
アエロジル社製)EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The abbreviations of the compounds used in the examples and the test methods are as follows. <Raw material>"E828": Bisphenol A type epoxy resin (manufactured by Yuka Shell Co., Ltd.) "E1001": Bisphenol A type epoxy resin (manufactured by Yuka Shell Co., Ltd.) "PN-23", "MY-24": Amine adduct type Latent curing agent (manufactured by Ajinomoto Co.) "HX-3722": Microcapsule type latent curing agent (manufactured by Asahi Kasei Co., Ltd.) [E828 / curing agent = 2/3 parts by weight masterbatch] DICY: dicyandiamide (manufactured by Yuka Shell Co., Ltd.) ) DCMU: 3- (3,4-dichlorophenyl) -1,1
-N dimethyl urea (manufactured by Hodogaya Chemical Co., Ltd.) "Arborex YS2", "YS3": Aluminum borate whiskers (manufactured by Shikoku Chemicals Co., Ltd.) <Aspect ratio = 10 to 60>"Whiscals": calcium carbonate whiskers ( Shikoku Kasei Co., Ltd.) <Aspect ratio = 20 to 60>"R202": Fine silica, Aerosil R202 (manufactured by Nippon Aerosil Co., Ltd.)
【0019】<レジンフローの測定>プリプレグを10
0×100mmに切断し、4プライ(ply)を積層、
上下を穴空きフィルム、最外層にガラスクロスを積層
後、加熱プレスで80℃、3.5kg/cm2 加圧し、
レジンフローを測定。<Measurement of resin flow> 10 prepregs
Cut to 0 x 100 mm and stack 4 plies,
After laminating the top and bottom perforated films and glass cloth on the outermost layer, press at 80 ° C and 3.5 kg / cm 2 with a heating press,
Measure the resin flow.
【0020】<捲回および炉落ちの評価>プリプレグを
斜交層(±45°)3ply、ストレート層(0°)3
plyとなる様に裁断した。裁断したプリプレグを離型
剤を塗布したマンドレルにローリングテーブルにより捲
回した。次いで熱収縮テープをテープラッビング装置に
より巻付けた。加熱炉に大径側を上にして吊下げ、80
℃/2時間硬化した。室温まで冷却後、炉落ちを測定。<Evaluation of Winding and Furnace Falling> A prepreg was formed in an oblique layer (± 45 °) 3 ply and a straight layer (0 °) 3
It was cut to be ply. The cut prepreg was wound on a mandrel coated with a release agent by a rolling table. The heat shrink tape was then wrapped with a tape rubbing device. Suspend in a heating furnace with the large diameter side up, 80
Hardened at ℃ / 2 hours. After cooling to room temperature, measure the furnace falling.
【0021】<取扱作業性:タック性、ドレープ性> (23℃における斜交層の貼合せ状態、修正の可否、手
巻きの硬さ、ローリングテーブル捲回後のハネ等より総
合的に判断) ○…良好、 ×…不良<Handling workability: tackiness, drapeability> (Comprehensive judgment based on the laminated state of the oblique layer at 23 ° C., correctability, manual winding hardness, shaving after rolling table winding, etc.) ○: good, ×: bad
【0022】<曲げ試験(3点曲げ)>ASTM D7
90に準じて、装置:東洋ボールドウィン社製UTM−
5Tを用い、サンプル形状:(長さ100mm,幅10
mm,厚さ2mm)、スパン長:80mm、クロスヘッ
ドスピード:2mm/minで測定。<Bending test (3-point bending)> ASTM D7
According to 90, device: UTM-made by Toyo Baldwin
Using 5T, sample shape: (length 100 mm, width 10
mm, thickness 2 mm), span length: 80 mm, crosshead speed: 2 mm / min.
【0023】<ILSS>ASTM D2344に準じ
て、同上装置により、サンプル形状:(長さ12mm、
幅10mm、厚さ2mm)、スパン長:8mm、クロス
ヘッドスピード:2mm/minで測定。<ILSS> According to ASTM D2344, sample shape: (length 12 mm,
Width 10 mm, thickness 2 mm), span length: 8 mm, crosshead speed: 2 mm / min.
【0024】(実施例1)「E828」を70重量部、
E1001を30重量部を150℃で30分間撹拌溶解
し、室温まで冷却してベースレジンを得た。このベース
レジンを55℃に加温し、攪拌機で「PN−23」を2
0重量部、アルボレックスYS2を5重量部を30分間
均一に撹拌混合して、本発明の樹脂組成物を得た。こう
して得られた樹脂組成物と炭素繊維(東レ社製、「トレ
カT300」、弾性率24ton/mm2 )とから一方
向プリプレグをホットメルト法で製造し、本発明のプリ
プレグを得た。このプリプレグの炭素繊維目付けは15
0g/m2 、樹脂量は35%であった。このプリプレグ
を一方向に14プライ積層し、オートクレーブで80℃
/2時間の硬化により約2mm厚の一方向積層板を成形
した。得られた複合材料の物性(Vf=60%換算値)
を表−1に示す。(Example 1) 70 parts by weight of "E828",
30 parts by weight of E1001 was dissolved by stirring at 150 ° C. for 30 minutes and cooled to room temperature to obtain a base resin. This base resin is heated to 55 ° C and the "PN-23" is mixed with a stirrer to 2
A resin composition of the present invention was obtained by uniformly stirring and mixing 0 part by weight and 5 parts by weight of Arbolex YS2 for 30 minutes. A unidirectional prepreg was produced from the resin composition thus obtained and carbon fiber (manufactured by Toray Industries, Inc., "Torayca T300", elastic modulus 24 ton / mm 2 ) by a hot melt method to obtain a prepreg of the present invention. The carbon fiber weight of this prepreg is 15
The resin amount was 0 g / m 2 and the resin amount was 35%. This ply prepreg is laminated in one direction with 14 plies and autoclaved at 80 ° C.
A unidirectional laminate having a thickness of about 2 mm was molded by curing for 2 hours. Physical properties of the obtained composite material (Vf = 60% conversion value)
Is shown in Table-1.
【0025】このプリプレグは、取扱作業性(タック、
ドレープ性)は良好であった。また得られたシャフト成
形品10本に炉落ちはまったくなかった。更に、この成
形品の表面を研磨機を用いて研磨し、表面の欠陥(キズ
等)について観察したが、すべて欠陥のない良好な成形
品を得られた。This prepreg is easy to handle (tack,
Drapability) was good. In addition, the 10 shaft molded products obtained did not have any furnace falling. Further, the surface of this molded product was polished with a polishing machine and observed for surface defects (scratches, etc.), and good molded products without any defects were obtained.
【0026】(実施例2、3、4、5)表1の組成によ
り、実施例1と同様の方法で本発明の樹脂組成物および
プリプレグを得た。このプリプレグの取扱作業性は良好
であり、また成形品に炉落ちはなく、研磨表面に欠陥は
観察されなかった。(Examples 2, 3, 4, 5) Using the compositions shown in Table 1, resin compositions and prepregs of the present invention were obtained in the same manner as in Example 1. The workability of this prepreg was good, the molded product did not fall off the furnace, and no defects were observed on the polished surface.
【0027】(比較例1)表−1の組成により、(C)
成分を用いなかった以外実施例1と同様の方法によりプ
リプレグを製造した。プリプレグの目付けは150g/
m2 で、樹脂量は35%であった。このプリプレグはタ
ック性が高く、取扱い性は不良であり、またレジンフロ
ーも大きく、炉落ちが発生した。また成形品研磨後のキ
ズの発生も顕著であった。(Comparative Example 1) According to the composition of Table-1, (C)
A prepreg was produced in the same manner as in Example 1 except that the components were not used. The basis weight of the prepreg is 150 g /
The resin amount was 35% in m 2 . This prepreg had high tackiness, poor handleability, and large resin flow, and the furnace fell. Further, the occurrence of scratches after polishing the molded product was remarkable.
【0028】(比較例2)無機充填剤として「エアロジ
ルR202」を用いた以外実施例1と同様にプリプレグ
を製造した。このプリプレグの作業性は比較的良好であ
ったが、炉落ちが発生し、成形品の表面にむらがあり、
また研磨後10本中数本にキズが発生した。Comparative Example 2 A prepreg was produced in the same manner as in Example 1 except that "Aerosil R202" was used as the inorganic filler. The workability of this prepreg was relatively good, but the furnace fell, and the surface of the molded product was uneven.
Also, after polishing, several scratches occurred out of 10 scratches.
【0029】(比較例3)表1の組成により、(B)成
分にDICYを4重量部、DCMUを4重量部を用い、
(C)成分を用いなかった以外実施例1と同様の方法に
よりプリプレグを製造した。取扱い作業性は不良であ
り、また硬化が不十分であり切削が出来なかった。Comparative Example 3 According to the composition shown in Table 1, 4 parts by weight of DICY and 4 parts by weight of DCMU were used as the component (B),
A prepreg was produced by the same method as in Example 1 except that the component (C) was not used. The workability was poor, and the hardening was insufficient so that cutting was not possible.
【0030】[0030]
【表1】 [Table 1]
【0031】[0031]
【発明の効果】本発明のウィスカーを含有したマトリッ
クス樹脂より製造されるプリプレグは、適度な作業性と
成形時のレジンフローを自由に調整することが可能であ
り、オーブン成形、内圧成形等の成形法で欠陥がなく、
また低温硬化が可能なため、大型成形にも適しており、
優れた複合材料特性を有する各種の成形体が得られる。
この様に、繊維強化複合材料の信頼性の向上、生産性の
向上、経済性の向上等にきわめて有益である。EFFECTS OF THE INVENTION The prepreg manufactured from the matrix resin containing the whiskers of the present invention can be appropriately adjusted in proper workability and resin flow at the time of molding, and can be molded by oven molding, internal pressure molding or the like. The law is flawless,
Also, since it can be cured at low temperature, it is also suitable for large-scale molding.
Various moldings having excellent composite material properties are obtained.
As described above, it is extremely useful for improving the reliability, productivity, and economic efficiency of the fiber-reinforced composite material.
Claims (6)
0.05〜30重量部 を含有することを特徴とするプリプレグ用エポキシ樹脂
組成物。1. The following components (A), (B) and (C): (B) 3 to 60 parts by weight of a low temperature active latent curing agent and (C) an aspect ratio of 3 to 100 parts by weight of an epoxy resin (A). The epoxy resin composition for prepregs, characterized by containing 0.05 to 30 parts by weight of the whiskers of 500 or less.
アダクト型の潜在性硬化剤であることを特徴とする請求
項1記載のエポキシ樹脂組成物。2. The epoxy resin composition according to claim 1, wherein the low temperature active latent curing agent (B) is an amine adduct type latent curing agent.
ロカプセル型の潜在性硬化剤であることを特徴とする請
求項1記載のエポキシ樹脂組成物。3. The epoxy resin composition according to claim 1, wherein the low temperature active latent curing agent (B) is a microcapsule type latent curing agent.
ムであることを特徴とする請求項1記載のエポキシ樹脂
組成物。4. The epoxy resin composition according to claim 1, wherein the whiskers (C) are aluminum borate.
あることを特徴とする請求項1記載のエポキシ樹脂組成
物。5. The epoxy resin composition according to claim 1, wherein the whiskers (C) are calcium carbonate.
ポキシ樹脂組成物を強化繊維に含浸してなることを特徴
とするプリプレグ。6. A prepreg obtained by impregnating a reinforcing fiber with the epoxy resin composition according to any one of claims 1 to 5.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15478794A JPH0820708A (en) | 1994-07-06 | 1994-07-06 | Epoxy resin composition and prepreg prepared therefrom |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15478794A JPH0820708A (en) | 1994-07-06 | 1994-07-06 | Epoxy resin composition and prepreg prepared therefrom |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0820708A true JPH0820708A (en) | 1996-01-23 |
Family
ID=15591896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15478794A Pending JPH0820708A (en) | 1994-07-06 | 1994-07-06 | Epoxy resin composition and prepreg prepared therefrom |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0820708A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09324107A (en) * | 1996-06-07 | 1997-12-16 | Matsushita Electric Ind Co Ltd | Electrically conductive filler composition |
KR100496040B1 (en) * | 1997-06-27 | 2005-10-12 | 주식회사 휴비스 | Manufacturing method of toughened epoxy resin using polyester waste chips |
US7294660B2 (en) * | 2002-06-14 | 2007-11-13 | Asahi Denka Co., Ltd. | Epoxy resin composition |
WO2012081407A1 (en) | 2010-12-13 | 2012-06-21 | 東レ株式会社 | Carbon fiber prepreg, method for producing same and carbon fiber reinforced composite material |
US8715543B2 (en) | 2011-03-31 | 2014-05-06 | Ocv Intellectual Capital, Llc | Microencapsulated curing agent |
EP2851182A1 (en) | 2013-09-20 | 2015-03-25 | New Era Materials Sp. z o.o. | 1-component system, products derived from same and method for the production of fibre compound semi-finished products components with the 1-component system |
US9315655B2 (en) | 2011-12-08 | 2016-04-19 | Ocv Intellectual Capital, Llc | Fiber reinforced resin molding compound and manufacturing method for fiber reinforced resin molded article therefrom |
US10040917B2 (en) | 2015-11-14 | 2018-08-07 | Leichtbau-Zentrum Sachsen Gmbh | 1C system, products to be manufactured from the system, and a method for manufacturing semifinished, fiber-reinforced products and components with the 1C system |
CN110684321A (en) * | 2018-07-05 | 2020-01-14 | Sk化学株式会社 | Epoxy resin composition for fiber-reinforced composite material and prepreg using same |
-
1994
- 1994-07-06 JP JP15478794A patent/JPH0820708A/en active Pending
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09324107A (en) * | 1996-06-07 | 1997-12-16 | Matsushita Electric Ind Co Ltd | Electrically conductive filler composition |
KR100496040B1 (en) * | 1997-06-27 | 2005-10-12 | 주식회사 휴비스 | Manufacturing method of toughened epoxy resin using polyester waste chips |
US7294660B2 (en) * | 2002-06-14 | 2007-11-13 | Asahi Denka Co., Ltd. | Epoxy resin composition |
WO2012081407A1 (en) | 2010-12-13 | 2012-06-21 | 東レ株式会社 | Carbon fiber prepreg, method for producing same and carbon fiber reinforced composite material |
US9074064B2 (en) | 2010-12-13 | 2015-07-07 | Toray Industries, Inc. | Carbon fiber prepreg, method for producing same and carbon fiber reinforced composite material |
US8715543B2 (en) | 2011-03-31 | 2014-05-06 | Ocv Intellectual Capital, Llc | Microencapsulated curing agent |
US9725575B2 (en) | 2011-03-31 | 2017-08-08 | Ocv Intellectual Capital, Llc | Microencapsulated curing agent |
US9315655B2 (en) | 2011-12-08 | 2016-04-19 | Ocv Intellectual Capital, Llc | Fiber reinforced resin molding compound and manufacturing method for fiber reinforced resin molded article therefrom |
EP2851182A1 (en) | 2013-09-20 | 2015-03-25 | New Era Materials Sp. z o.o. | 1-component system, products derived from same and method for the production of fibre compound semi-finished products components with the 1-component system |
US10040917B2 (en) | 2015-11-14 | 2018-08-07 | Leichtbau-Zentrum Sachsen Gmbh | 1C system, products to be manufactured from the system, and a method for manufacturing semifinished, fiber-reinforced products and components with the 1C system |
CN110684321A (en) * | 2018-07-05 | 2020-01-14 | Sk化学株式会社 | Epoxy resin composition for fiber-reinforced composite material and prepreg using same |
CN110684321B (en) * | 2018-07-05 | 2024-01-09 | 东丽先端素材株式会社 | Epoxy resin composition for fiber reinforced composite material and prepreg using same |
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