JPH0971633A - Epoxy resin composition for prepreg - Google Patents
Epoxy resin composition for prepregInfo
- Publication number
- JPH0971633A JPH0971633A JP23051195A JP23051195A JPH0971633A JP H0971633 A JPH0971633 A JP H0971633A JP 23051195 A JP23051195 A JP 23051195A JP 23051195 A JP23051195 A JP 23051195A JP H0971633 A JPH0971633 A JP H0971633A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- prepreg
- weight
- molded product
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、成形品表面のピン
ホールの発生および成型品内部のボイドの発生を抑制で
きるプリプレグ用エポキシ樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition for prepreg which can suppress the generation of pinholes on the surface of molded products and the generation of voids inside the molded products.
【０００２】[0002]
【従来の技術】強化繊維にエポキシ樹脂を含浸しシート
状としたプリプレグは、繊維強化複合材料の中間材料と
して、航空機用途から釣竿、ゴルフシャフト等の汎用用
途まで広く用いられている。このプリプレグには、大別
して、強化繊維を１方向に引き揃えマトリクス樹脂を含
浸したＵＤプリプレグと製織した強化繊維織布にマトリ
クス樹脂を含浸したクロスプリプレグがある。2. Description of the Related Art Sheet-like prepregs made by impregnating reinforcing fibers with epoxy resin are widely used as intermediate materials for fiber-reinforced composite materials, from aircraft applications to general-purpose applications such as fishing rods and golf shafts. This prepreg is roughly classified into a UD prepreg in which reinforcing fibers are aligned in one direction and impregnated with a matrix resin, and a cross prepreg in which a woven woven reinforced fiber is impregnated with a matrix resin.
【０００３】特に、クロスプリプレグは、大型成形物用
途などで広く用いられているのみならず、成形表面に現
れる綺麗な織り目模様を利用した意匠性材料としても市
場のニーズが高まっている。しかしクロスプリプレグを
用いた成形物は、成形品の表面のピンホールと呼ばれる
欠陥や成形品内部のボイドが発生しやすく、後加工によ
る修正の必要が多いため、その改善が望まれている。In particular, the cloth prepreg is not only widely used in applications such as large moldings, but also in the market as a designable material utilizing a beautiful texture pattern appearing on the molding surface. However, the molded product using the cross prepreg is apt to cause defects called pinholes on the surface of the molded product and voids inside the molded product, and it is necessary to correct it by post-processing, and therefore improvement thereof is desired.
【０００４】また、ＵＤプリプレグでは、成形品表面の
ピンホールの発生はほとんど問題にならないが、強度面
で成形品内部のボイドの発生は重大な問題である。Further, in the UD prepreg, the generation of pinholes on the surface of the molded product is hardly a problem, but the generation of voids inside the molded product is a serious problem in terms of strength.
【０００５】一般にこのような成形品表面のピンホール
の発生、成形品内部のボイドの発生は成形方法や成形条
件などに大きく依存することが知られており、従来は成
形方法や成形条件を最適化することによりピンホール、
ボイドの減少する努力がなされてきた。しかし、成形条
件の最適化により良好な成形品が得られる場合でも、そ
の最適な条件の幅は非常に狭いため、熟練工の技術に依
存することころが多く、安定して生産することが難しい
のが現状である。また、マトリックス樹脂の特性を適性
化することにより外観不良を抑制する試みも一部では検
討されているが、満足する結果が得られていないのが現
状である。It is generally known that the generation of pinholes on the surface of a molded product and the generation of voids inside the molded product largely depend on the molding method and molding conditions. Conventionally, the molding method and molding conditions have been optimized. Pinholes,
Efforts have been made to reduce voids. However, even if a good molded product can be obtained by optimizing the molding conditions, the range of the optimum conditions is very narrow, so that it often depends on the skill of skilled workers, and it is difficult to produce stably. The current situation. In addition, some attempts have been made to suppress appearance defects by optimizing the characteristics of the matrix resin, but at present, satisfactory results have not been obtained.
【０００６】[0006]
【発明が解決しようとする課題】本発明は室温でのタッ
ク、ドレープ性、保存安定性を犠牲にすることなく、成
型品表面のピンホールの発生および成型品内部のボイド
の発生を抑制できるプリプレグ用エポキシ樹脂組成物を
提供することにある。DISCLOSURE OF THE INVENTION The present invention provides a prepreg capable of suppressing the generation of pinholes on the surface of a molded product and the generation of voids inside the molded product without sacrificing tack, drape property and storage stability at room temperature. An epoxy resin composition for use.
【０００７】上記課題を解決するために、クロスプリプ
レグ成形品のピンホールやボイドの発生とマトリックス
樹脂組成の関係について鋭意研究した結果、成型品表面
のピンホールや成型品内部のボイドの原因となるプリプ
レグ内部に含まれるあるいは積層時にトラップされた気
泡を成形中に効率よく外部に排出できるエポキシ樹脂組
成物を見いだし本発明に到達した。In order to solve the above-mentioned problems, as a result of earnest research on the relationship between the generation of pinholes and voids in the cross prepreg molded product and the matrix resin composition, pinholes on the surface of the molded product and voids inside the molded product are caused. The present invention has been accomplished by finding an epoxy resin composition capable of efficiently discharging bubbles contained in the prepreg or trapped during lamination to the outside during molding.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明の要旨
は、（Ａ）ノボラック型エポキシ樹脂１０〜５０重量
％、（Ｂ）ビスフェノールＦ型固形エポキシ樹脂２０〜
５０重量％、（Ｃ）２５℃で１０〜２５０ポイズのエポ
キシ樹脂２０〜４０重量％、（Ｄ）（Ａ）〜（Ｃ）に溶
解する熱可塑性樹脂１〜１０重量％および（Ｅ）ジシア
ンジアミド２〜１５重量％を必須成分とし、上記
（Ａ）、（Ｂ）、（Ｃ）成分の重量比が（Ｂ）／（Ａ）
＝０．２〜３．０、（Ｃ）／（Ａ）＝０．２〜３．０で
あるプリプレグ用エポキシ樹脂組成物にある。That is, the gist of the present invention is (A) 10 to 50% by weight of a novolac type epoxy resin, and (B) a bisphenol F type solid epoxy resin 20 to 20% by weight.
50% by weight, (C) 20 to 40% by weight of epoxy resin having 10 to 250 poise at 25 ° C., (D) 1 to 10% by weight of thermoplastic resin soluble in (A) to (C), and (E) dicyandiamide 2 To 15% by weight as an essential component, and the weight ratio of the components (A), (B) and (C) is (B) / (A).
= 0.2 to 3.0, (C) / (A) = 0.2 to 3.0, the epoxy resin composition for prepreg.
【０００９】[0009]
【発明の実施の形態】以下本発明についてさらに詳しく
述べる。成型品内部ボイドや成型品表面のピンホールが
発生する原因は、プリプレグ内部から発生する気泡が層
間や表面に溜まることにより生じると考えられる。ＵＤ
プリプレグと比較して、気泡が溜まりやすい織り目を有
するクロスプリプレグの成形品は、ボイドや成型品表面
のピンホールが発生し易いのはこのためである。この成
型品内部のボイドや成型品表面のピンホールの原因とな
るプリプレグ内部から発生する気泡は、主にマトリック
ス樹脂に含まれる細かい気泡や、強化繊維中のマトリク
スが未含浸部に存在する気体、積層時に層間に咬んだ気
泡と考えられる。The present invention will be described in more detail below. The cause of the voids inside the molded product and the pinholes on the surface of the molded product is considered to be caused by the accumulation of air bubbles generated from the inside of the prepreg between the layers and the surface. UD
This is why voids and pinholes on the surface of the molded product are more likely to occur in the molded product of the cross prepreg having a texture in which air bubbles tend to accumulate, as compared with the prepreg. Bubbles generated from the inside of the prepreg that causes voids inside this molded product and pinholes on the surface of the molded product are fine bubbles mainly contained in the matrix resin, and the gas in which the matrix in the reinforcing fiber exists in the unimpregnated part, It is considered that the bubbles were bitten between the layers during stacking.
【００１０】従って、ボイドや成型品表面のピンホール
は、プリプレグ内部、プリプレグの積層体の中の気泡の
量を減少する、もしくは気泡、気体を成形中に積層体外
部に排出することにより抑制できると考えられる。Therefore, voids and pinholes on the surface of the molded product can be suppressed by reducing the amount of bubbles inside the prepreg or in the laminate of the prepreg, or by discharging bubbles or gas to the outside of the laminate during molding. it is conceivable that.
【００１１】本発明のエポキシ樹脂は、上記のピンホー
ル、ボイドの発生抑制メカニズムのうち後者の、気泡を
成形中に積層体外部に排出するメカニズムに有利なプリ
プレグ用エポキシ樹脂組成物である。The epoxy resin of the present invention is an epoxy resin composition for prepreg, which is advantageous in the latter mechanism of suppressing the generation of pinholes and voids, which is the mechanism of discharging bubbles to the outside of the laminate during molding.
【００１２】本発明の（Ａ）成分であるノボラック型エ
ポキシ樹脂とは、樹脂の主な骨格がフェノールノボラッ
ク型、もしくはフェノールノボラック型エポキシ樹脂を
主成分とするエポキシ樹脂を指し、具体的にはフェノー
ルノボラック、クレゾールノボラック等のフェノールノ
ボラックをグリシジル化した化合物があげられる。ま
た、これらグリシジル化合物を可塑性などの付与のため
に変性した樹脂を用いても構わない。もちろんフェノー
ルノボラックを何らかの手法で変性した後、グリシジル
化しても構わない。さらに、これらを単独で用いても２
種類以上を組み合わせて用いても構わない。The novolak type epoxy resin which is the component (A) of the present invention refers to an epoxy resin whose main skeleton is a phenol novolac type or an epoxy resin whose main component is a phenol novolac type epoxy resin. Examples thereof include compounds in which phenol novolac such as novolac and cresol novolac are glycidylated. A resin obtained by modifying these glycidyl compounds for imparting plasticity may be used. Of course, the phenol novolac may be modified by some method and then converted into glycidyl. Furthermore, even if these are used alone, 2
A combination of more than one type may be used.
【００１３】（Ａ）成分のフェノールノボラック型エポ
キシ樹脂としてフェノールノボラック類をグリシジル化
して使用するほか、市販のものも使用できる。例えば、
大日本インキ化学工業株式会社製の Ｎ−６６０シリー
ズ、Ｎ−７３０、Ｎ−７４０、Ｎ−７７０シリーズ、Ｎ
−８６５，Ｎ−５１０，ＳＩＮ−６２０，ＥＸＡ−１８
５７Ｔ，ＥＸＡ−４５０６，ＥＸＡ−４３００などの変
性ノボラック樹脂、油化シェルエポキシ株式会社製のＥ
ｐ１５２、Ｅｐ１５４，Ｅｐ１５７シリーズ、Ｅｐ１８
０シリーズなど、日本チバガイギー株式会社製のＥＰＮ
１１３９シリーズが例示できるが、これらに限定される
ものではない。As the phenol novolac type epoxy resin as the component (A), phenol novolacs can be glycidylated and used, or commercially available ones can also be used. For example,
Dainippon Ink and Chemicals, Inc. N-660 series, N-730, N-740, N-770 series, N
-865, N-510, SIN-620, EXA-18
57T, EXA-4506, modified novolac resins such as EXA-4300, E manufactured by Yuka Shell Epoxy Co., Ltd.
p152, Ep154, Ep157 series, Ep18
EPN manufactured by Japan Ciba-Geigy Co., Ltd.
The 1139 series can be exemplified, but the invention is not limited thereto.
【００１４】また、樹脂組成物の粘度の調整などのため
に（Ａ）成分としてノボラック型エポキシ樹脂と他のエ
ポキシ樹脂を混合して用いても、ノボラック型エポキシ
樹脂が（Ａ）成分の７０％重量以上であり、ボイドおよ
び成型品表面のピンホールの発生の抑制を阻害しないも
のであるならば構わない。この時使用できるエポキシ樹
脂については特には限定しない。Even if a novolac type epoxy resin is mixed with another epoxy resin as the component (A) for adjusting the viscosity of the resin composition, the novolac type epoxy resin is 70% of the component (A). It does not matter as long as it is not less than the weight and does not inhibit the suppression of generation of voids and pinholes on the surface of the molded product. The epoxy resin that can be used at this time is not particularly limited.
【００１５】（Ａ）成分の含有量は、（Ａ）から（Ｄ）
の混合樹脂中に１０〜５０重量％である。更に好ましく
は１５〜４５重量％である。添加量が１０重量％未満あ
るいは５０重量％を超える場合は、他の構成成分とのバ
ランスが崩れ、ボイドおよび成型品表面のピンホールの
発生を抑制する効果が得られない。The content of the component (A) varies from (A) to (D).
10 to 50% by weight in the mixed resin of. More preferably, it is 15 to 45% by weight. If the addition amount is less than 10% by weight or more than 50% by weight, the balance with other components is lost, and the effect of suppressing the generation of voids and pinholes on the surface of the molded product cannot be obtained.
【００１６】本発明のプリプレグ用エポキシ樹脂中の
（Ｂ）成分で用いるビスフェノールＦ型エポキシ樹脂は
室温において固形であることが必要であり、軟化点が５
０℃〜１３０℃であることがさらに好ましい。軟化点が
５０℃未満であると（Ｂ）成分としての添加効果が得ら
れない傾向にある。軟化点が１３０℃を超えるとプリプ
レグとした時のドレープ性が失われる傾向にある。The bisphenol F type epoxy resin used as the component (B) in the epoxy resin for prepreg of the present invention needs to be solid at room temperature and has a softening point of 5
More preferably, it is 0 ° C to 130 ° C. If the softening point is less than 50 ° C, the effect of addition as the component (B) tends to be unobtainable. If the softening point exceeds 130 ° C., the drapability of the prepreg tends to be lost.
【００１７】（Ｂ）成分のビスフェノールＦ型固形エポ
キシ樹脂は市販されているものを用いても、以下の合成
方法で合成したものを用いても構わない。合成方法とし
ては、市販されている低粘度のビスフェノールＦ型エポ
キシ樹脂にジアミノジフェニルメタン、ジアミノジフェ
ニルサルフォンといった硬化剤を適量配合し、反応させ
ることにより得ることができる。得られるビスフェノー
ルＦ型固形エポキシ樹脂の軟化点は硬化剤の添加量や反
応を制御することにより調節される。The bisphenol F type solid epoxy resin as the component (B) may be a commercially available one or one synthesized by the following synthesis method. As a synthesizing method, a commercially available low-viscosity bisphenol F type epoxy resin is mixed with an appropriate amount of a curing agent such as diaminodiphenylmethane or diaminodiphenylsulfone, and the mixture is reacted. The softening point of the obtained bisphenol F type solid epoxy resin is adjusted by controlling the addition amount of the curing agent and the reaction.
【００１８】一般に市販品として入手可能なものとして
は、油化シェルエポキシ株式会社製のＥ４００１ｐシリ
ーズが挙げられるがこれらに限定されるものではない。
本発明の（Ｂ）成分であるビスフェノールＦ型固形エポ
キシ樹脂の含有量は、成分（Ａ）から（Ｄ）の樹脂中に
２０〜５０重量％であることが必要であり、更に好まし
くは２５〜４５重量％である。この添加量の範囲外で
は、エポキシ樹脂組成物の成形中における粘度のバラン
スが崩れ本発明の目的を達成できない。Generally, commercially available products include, but are not limited to, E4001p series manufactured by Yuka Shell Epoxy Co., Ltd.
The content of the bisphenol F type solid epoxy resin which is the component (B) of the present invention is required to be 20 to 50% by weight in the resin of the components (A) to (D), and more preferably 25 to It is 45% by weight. If the amount added is outside this range, the viscosity balance of the epoxy resin composition during molding will be lost and the object of the present invention will not be achieved.
【００１９】（Ｃ）成分としては、２５℃での粘度が１
〜２５０ポイズであるエポキシ樹脂がであることが必要
である。樹脂組成物中に（Ｃ）成分の低粘度樹脂が存在
することにより、プリプレグ内部から発生する気泡を抑
制する働きが期待できる。The component (C) has a viscosity of 1 at 25 ° C.
It is necessary that the epoxy resin be ~ 250 poise. The presence of the low-viscosity resin as the component (C) in the resin composition can be expected to have a function of suppressing bubbles generated inside the prepreg.
【００２０】（Ｃ）成分の含有量は、（Ａ）から（Ｄ）
の樹脂中に２０〜４０重量％であることが必要である。
この範囲をはずれると、樹脂組成物のバランスが崩れ、
本発明の目的を達成し得ない。The content of the component (C) varies from (A) to (D).
It is necessary to be 20 to 40% by weight in the resin.
Out of this range, the balance of the resin composition is lost,
The object of the present invention cannot be achieved.
【００２１】（Ｃ）成分として使用できるエポキシ樹脂
としては、上記の粘度、添加量の範囲であれば、いかな
るエポキシ樹脂を用いても構わない。２種類以上のエポ
キシ樹脂を組み合わせ、上記の樹脂粘度に調整して用い
ても構わない。As the epoxy resin which can be used as the component (C), any epoxy resin may be used as long as it has the above-mentioned viscosity and addition amount. Two or more kinds of epoxy resins may be combined and adjusted to the above resin viscosity before use.
【００２２】（Ｃ）成分として使用できるエポキシ樹脂
としては、グリシジルエーテル系エポキシ樹脂、ビスフ
ェノールＡ型、ビスフェノールＦ型エポキシ樹脂、環式
脂肪族エポキシ樹脂、グリシジルエステル系エポキシ樹
脂、グリシジルアミン系エポキシ樹脂、および複素環式
エポキシ樹脂、飽和もしくは不飽和アルキル骨格を有す
るエポキシ樹脂およびこれらを変性したエポキシ樹脂が
挙げられるが上記粘度範囲を満足するものであればこれ
らに限定されるものではない。As the epoxy resin which can be used as the component (C), glycidyl ether type epoxy resin, bisphenol A type, bisphenol F type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, And a heterocyclic epoxy resin, an epoxy resin having a saturated or unsaturated alkyl skeleton, and an epoxy resin modified with these, but the epoxy resin is not limited to these as long as the viscosity range is satisfied.
【００２３】本発明における（Ｄ）成分は、（Ａ）、
（Ｂ）、（Ｃ）成分のエポキシ樹脂の何れに対しても溶
解する熱可塑性樹脂であることが必要である。この熱可
塑性樹脂として好適に用いられる樹脂としてはポリビニ
ルアセタール樹脂やフェノキシ樹脂である。ポリビニル
アセタール樹脂としてはポリビニルブチラールまたはポ
リビニルホルマールが好適に用いられるが、ビニルアセ
タール部、ビニルアルコール部、およびビニルアセテー
ト部からなり、ビニルアセタール部が７０％以上含ま
れ、平均重合度が７００〜２０００であることが好まし
い。The component (D) in the present invention is (A),
It is necessary that the thermoplastic resin is soluble in both the epoxy resins of the components (B) and (C). The resin preferably used as the thermoplastic resin is a polyvinyl acetal resin or a phenoxy resin. Although polyvinyl butyral or polyvinyl formal is preferably used as the polyvinyl acetal resin, it is composed of a vinyl acetal part, a vinyl alcohol part, and a vinyl acetate part, and contains 70% or more of the vinyl acetal part and has an average degree of polymerization of 700 to 2000. Preferably there is.
【００２４】（Ｄ）成分の熱可塑性樹脂の含有量は、
（Ａ）から（Ｄ）の樹脂中に１〜１０重量％であること
が必要であり、更に好ましくは２〜６重量％である。添
加量は１０重量％を超えると、樹脂組成物の粘度が上昇
し、タックおよびドレープ性が低下し、１重量％未満で
あると添加によるボイドおよび成型品表面のピンホール
の発生を抑制する効果が得られない。The content of the thermoplastic resin as the component (D) is
It is necessary to be 1 to 10% by weight in the resin (A) to (D), and more preferably 2 to 6% by weight. If the addition amount exceeds 10% by weight, the viscosity of the resin composition increases, and the tack and drape properties decrease, and if it is less than 1% by weight, the effect of suppressing the generation of voids and pinholes on the surface of the molded product due to the addition Can't get
【００２５】本発明の（Ｅ）成分であるエポキシ樹脂の
硬化剤はジシアンジアミドであることが成型品の高い力
学特性を得る点で必要である。（Ｅ）成分の添加量は２
〜１５重量％であることが必要である。１５重量％を超
えると保存安定性が得られず、２重量％未満であると十
分に硬化進行しない場合が生じる。また、ジシアンジア
ミドには、硬化促進剤を併用することが成形温度が低く
抑えることができるので好ましい。硬化促進剤としては
ジクロロフェニルジメチルウレアなどの尿素化合物、イ
ミダゾール類、３級アミン化合物などが例示できるがこ
れに限定するものではない。The curing agent for the epoxy resin which is the component (E) of the present invention is required to be dicyandiamide in order to obtain high mechanical properties of the molded product. The amount of component (E) added is 2
It needs to be １５15% by weight. If it exceeds 15% by weight, storage stability cannot be obtained, and if it is less than 2% by weight, curing may not proceed sufficiently. Further, it is preferable to use a curing accelerator in combination with dicyandiamide because the molding temperature can be kept low. Examples of the curing accelerator include, but are not limited to, urea compounds such as dichlorophenyldimethylurea, imidazoles, and tertiary amine compounds.
【００２６】さらに本発明のプリプレグ用エポキシ樹脂
組成物において、重要な要素は上述したエポキシ樹脂成
分（Ａ）、（Ｂ）、（Ｃ）を重量比で、（Ｂ）／（Ａ）
＝０．２〜３．５、（Ｃ）／（Ａ）＝０．２〜３．５と
することであり、（Ｂ）／（Ａ）＝０．４〜２．５、
（Ｃ）／（Ａ）＝０．２〜２．５がさらに好ましい。Further, in the epoxy resin composition for prepreg of the present invention, an important factor is the weight ratio of the above-mentioned epoxy resin components (A), (B) and (C), (B) / (A).
= 0.2 to 3.5, (C) / (A) = 0.2 to 3.5, and (B) / (A) = 0.4 to 2.5,
(C) / (A) = 0.2 to 2.5 is more preferable.
【００２７】エポキシ樹脂成分（Ａ）、（Ｂ）、（Ｃ）
が上記重量比で配合されていることにより、プリプレグ
のタックドレープ性といった取扱い性、成型品の機械的
特性を犠牲にすることなく、成形時の粘度挙動を制御
し、ボイドおよびピンホールの原因となるプリプレグ内
部から発生する気泡を効率よく外部に排出でき、ボイド
およびピンホールの発生を抑制することができるのであ
る。Epoxy resin components (A), (B), (C)
By blending in the above weight ratio, the viscosity behavior during molding is controlled without sacrificing handleability such as tack drape of the prepreg and mechanical properties of the molded product, and the cause of voids and pinholes The bubbles generated from the inside of the prepreg can be efficiently discharged to the outside, and the generation of voids and pinholes can be suppressed.
【００２８】さらに、上述したエポキシ樹脂組成物に他
の特性を犠牲にしない範囲で、消泡剤として上市されて
いる、ボイドおよび成型品表面のピンホールの原因とな
る気泡を成型品の外部に排出しやすくする添加剤を併用
しても構わない。Further, to the outside of the molded product, voids and marketed pinholes on the surface of the molded product, which are marketed as an antifoaming agent, are provided to the outside of the molded product within a range in which other properties are not sacrificed. You may use together the additive which makes it easy to discharge.
【００２９】脱泡剤は樹脂組成物１００重量部に対して
０．３〜２重量部が好ましい。より好ましくは０．５〜
１．５重量部である。脱泡剤は本発明のエポキシ樹脂組
成物と比較的相溶性の低いのもが好適で、かつ気泡の自
由エネルギーを低下させる界面活性剤的な働きを有する
物が好ましいが、これらに限定するものではない。The defoaming agent is preferably 0.3 to 2 parts by weight with respect to 100 parts by weight of the resin composition. More preferably 0.5-
It is 1.5 parts by weight. It is preferable that the defoaming agent has a relatively low compatibility with the epoxy resin composition of the present invention, and it is preferable that the defoaming agent has a function as a surfactant that lowers the free energy of bubbles, but is not limited thereto. is not.
【００３０】また、本発明のプリプレグ用エポキシ樹脂
組成物は、３０℃で１０5〜５×１０7ポイズの粘度であ
ることが好ましい。１０5ポイズ未満であると、その樹
脂組成物を用いたプリプレグはべたつき取扱いづらく、
５×１０7ポイズを超えるとプリプレグのドレープ性が
失われるので好ましくない。The epoxy resin composition for prepreg of the present invention preferably has a viscosity of 10 5 to 5 × 10 7 poise at 30 ° C. If it is less than 10 5 poise, the prepreg using the resin composition is not sticky and is difficult to handle.
If it exceeds 5 × 10 7 poise, the drape property of the prepreg is lost, which is not preferable.
【００３１】[0031]
【実施例】以下、実施例により本発明を更に具体的に説
明する。The present invention will be described in more detail with reference to the following examples.
【００３２】（実施例１〜１０、比較例１〜６）１３０
℃の油浴中に固定したセパラブルフラスコに成分
（Ａ）、（Ｂ）、（Ｃ）および（Ｄ）を表１に示したそ
れぞれの量比で順に投入し撹拌翼で混合し、溶解を確認
した後、冷却した。８０℃まで冷めたところで、さらに
（Ｅ）、３，４−ジクロルフェニル−Ｎ，Ｎ−ジメチル
尿素を加え撹拌翼で十分に混合した。室温に冷ました前
記樹脂を離型紙上にドクターナイフを用い樹脂目付１６
２ｇ／ｍ2の樹脂フィルムとした。次にこの樹脂フィル
ム上に弾性率２４トン／ｍｍ2の炭素繊維を１２．５本
／インチで平織りした三菱レイヨン株式会社製ＣＦクロ
ス（品番：ＴＲ３１１０、目付２００ｇ／ｍ2）とポリ
プロピレンフィルムをかさねた後、表面温度９０℃のロ
ール対の間を通してクロスプリプレグを作製した。樹脂
含有率は約４５wt％であった。(Examples 1 to 10 and Comparative Examples 1 to 6) 130
Components (A), (B), (C) and (D) were placed in a separable flask fixed in an oil bath at 0 ° C in the respective quantitative ratios shown in Table 1 and mixed with a stirring blade to dissolve the components. After checking, it cooled. After cooling to 80 ° C., (E) and 3,4-dichlorophenyl-N, N-dimethylurea were further added and thoroughly mixed with a stirring blade. Cool the resin to room temperature and put the resin on the release paper using a doctor knife.
The resin film was 2 g / m 2 . Next, on this resin film, CF cloth (product number: TR3110, unit weight: 200 g / m 2 ) manufactured by Mitsubishi Rayon Co., Ltd., which was plain-woven with carbon fiber having an elastic modulus of 24 tons / mm 2 at 12.5 fibers / inch, and a polypropylene film were covered. After that, a cross prepreg was produced by passing between the roll pair having a surface temperature of 90 ° C. The resin content was about 45 wt%.
【００３３】このクロスプリプレグのタック、ドレープ
性、保存安定性と真空バック、オートクレーブ、プレス
成型法で各々成形した成形品のボイドおよび外観の評価
結果を表１に示した。Table 1 shows the evaluation results of voids and appearances of the molded articles which were molded by tack, drape, storage stability, vacuum bag, autoclave, and press molding method of this cross prepreg.
【００３４】なお、層間のボイドおよび成型品表面のピ
ンホールは以下のように評価した。 （ボイドおよび外観の評価）下記に示す成形方法および
成形条件で成形して得られるコンポジット板（７ｃｍ×
７ｃｍ）についてボイドおよび成型品表面のピンホール
の評価を実施した。ボイドの評価は成形品の断面部（１
００ｍｍ2）に存在するボイドの数を顕微鏡を用い肉眼
で計数した。表面のピンホールの量は、成形品中央の５
ｃｍ2中に存在するピンホールを肉眼で計数した。The voids between the layers and the pinholes on the surface of the molded product were evaluated as follows. (Evaluation of Void and Appearance) A composite plate (7 cm ×) obtained by molding under the molding method and molding conditions shown below.
7 cm) was evaluated for voids and pinholes on the surface of the molded product. The evaluation of voids is performed by using the cross-section (1
The number of voids present at 00 mm 2 ) was counted with the naked eye using a microscope. The amount of pinholes on the surface is 5 at the center of the molded product.
The pinholes present in cm 2 were counted visually.
【００３５】（プリプレグのタックおよびドレープ性）
触感テストにより評価した。(Tack and drape of prepreg)
It was evaluated by a tactile test.
【００３６】（プリプレグの保存安定性評価）プリプレ
グを２５℃で１カ月保管した後のタックおよびドレープ
性を感触テストにより評価した。(Evaluation of Storage Stability of Prepreg) The prepreg was stored at 25 ° C. for 1 month, and the tack and drape properties were evaluated by a feel test.
【００３７】（成形方法および成形条件） 真空バック成形法 離型剤を塗布した厚さ２ｍｍの鉄板上に７ｃｍ×７ｃｍ
に切断したクロスプリプレグを５枚積層し、その上に離
型剤を塗布したＰＥＴフィルム、ガラス繊維不織布をの
せ、その上からナイロンフィルムでバックした。その内
部を真空ポンプで減圧した後、１．５℃／分で昇温し、
１２０℃に２時間保持して成形した。(Molding Method and Molding Conditions) Vacuum Back Molding Method 7 cm × 7 cm on a 2 mm thick iron plate coated with a release agent.
Five pieces of the cross prepreg cut into were laminated, and a PET film coated with a release agent and a glass fiber non-woven fabric were placed thereon, and a nylon film was used as a back from above. After depressurizing the inside with a vacuum pump, the temperature was raised at 1.5 ° C / min.
Molding was carried out by holding at 120 ° C. for 2 hours.
【００３８】オートクレーブ成形法 離型剤を塗布した厚さ２ｍｍの鉄板上に７ｃｍ×７ｃｍ
に切断したクロスプリプレグを５枚積層し、その上に離
型剤を塗布したＰＥＴフィルム、ガラス繊維不織布をの
せ、その上からナイロンフィルムでバックした。オート
クレーブ内でその内部を真空ポンプで減圧、窒素ガスに
より５ｋｇ／ｃｍ2に加圧しながら、１．５℃／分で昇
温し、１２０℃に２時間保持して成形した。Autoclave molding method 7 cm × 7 cm on a 2 mm thick iron plate coated with a release agent.
Five pieces of the cross prepreg cut into were laminated, and a PET film coated with a release agent and a glass fiber non-woven fabric were placed thereon, and a nylon film was used as a back from above. The inside of the autoclave was depressurized by a vacuum pump and pressurized to 5 kg / cm 2 with nitrogen gas, heated at 1.5 ° C / min, and held at 120 ° C for 2 hours for molding.
【００３９】プレス成形 離型剤を塗布した厚さ２ｍｍの鉄板上に７ｃｍ×７ｃｍ
に切断したクロスプリプレグを５枚積層したものを厚さ
１０ｍｍの鉄板で上下から挟み、あらかじめ１２０℃に
加熱したプレス機セットし、圧力２０ｋｇ／ｃｍ2下に
２時間放置して成型品を得た。Press molding 7 cm × 7 cm on a 2 mm thick iron plate coated with a release agent.
A stack of 5 pieces of cross prepreg cut into pieces was sandwiched between 10 mm thick iron plates from above and below, and the press machine was preheated to 120 ° C. and set to leave a pressure of 20 kg / cm 2 for 2 hours to obtain a molded product. .
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【発明の効果】本発明のエポキシ樹脂組成物をプリプレ
グのマトリックス樹脂として用いることにより、プリプ
レグのタック、ドレープ性、保存安定性、および、成形
後の機械的特性を犠牲にすることなく、層間のボイドお
よび成型品表面のピンホールの発生を抑制することが可
能となる。EFFECT OF THE INVENTION By using the epoxy resin composition of the present invention as a matrix resin for a prepreg, it is possible to obtain a good adhesion between the layers without sacrificing the tack, drape, storage stability, and mechanical properties after molding of the prepreg. It is possible to suppress the generation of voids and pinholes on the surface of the molded product.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 加藤 和夫 愛知県名古屋市東区砂田橋四丁目１番60号 三菱レイヨン株式会社商品開発研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuo Kato 4-60 Sunadabashi, Higashi-ku, Nagoya, Aichi Prefecture Mitsubishi Rayon Co., Ltd. Product Development Laboratory
Claims (1)
５０重量％、（Ｂ）ビスフェノールＦ型固形エポキシ樹
脂２０〜５０重量％、（Ｃ）２５℃で１０〜２５０ポイ
ズのエポキシ樹脂２０〜４０重量％、（Ｄ）（Ａ）〜
（Ｃ）に溶解する熱可塑性樹脂１〜１０重量％および
（Ｅ）ジシアンジアミド２〜１５重量％を必須成分と
し、上記（Ａ）、（Ｂ）、（Ｃ）成分の重量比が（Ｂ）
／（Ａ）＝０．２〜３．０、（Ｃ）／（Ａ）＝０．２〜
３．０であるプリプレグ用エポキシ樹脂組成物。1. (A) Novolac type epoxy resin 10
50% by weight, (B) 20 to 50% by weight of bisphenol F type solid epoxy resin, (C) 20 to 40% by weight of epoxy resin of 10 to 250 poise at 25 ° C., (D) (A) to
1 to 10% by weight of a thermoplastic resin soluble in (C) and 2 to 15% by weight of (E) dicyandiamide are essential components, and the weight ratio of the components (A), (B) and (C) is (B).
/(A)=0.2 to 3.0, (C) / (A) = 0.2 to
The epoxy resin composition for prepregs which is 3.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23051195A JP3634902B2 (en) | 1995-09-07 | 1995-09-07 | Epoxy resin composition for prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23051195A JP3634902B2 (en) | 1995-09-07 | 1995-09-07 | Epoxy resin composition for prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0971633A true JPH0971633A (en) | 1997-03-18 |
| JP3634902B2 JP3634902B2 (en) | 2005-03-30 |
Family
ID=16908905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23051195A Expired - Lifetime JP3634902B2 (en) | 1995-09-07 | 1995-09-07 | Epoxy resin composition for prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3634902B2 (en) |
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|---|---|---|---|---|
| WO2007088889A1 (en) | 2006-02-03 | 2007-08-09 | Asahi Kasei Chemicals Corporation | Microcapsule type hardener for epoxy resin, masterbatch type hardener composition for epoxy resin, one-pack type epoxy resin composition, and processed article |
| JP2010001403A (en) * | 2008-06-20 | 2010-01-07 | Taiyo Ink Mfg Ltd | Thermosetting resin composition |
| CN103183932A (en) * | 2011-12-29 | 2013-07-03 | 邓禄普体育用品株式会社 | Tubular body made of fiber-reinforced epoxy resin material |
| WO2014021386A1 (en) | 2012-07-31 | 2014-02-06 | 旭化成イーマテリアルズ株式会社 | Epoxy resin composition, epoxy resin, and cured article |
| WO2014069576A1 (en) * | 2012-10-31 | 2014-05-08 | ダンロップスポーツ株式会社 | Fiber-reinforced epoxy resin material, prepreg, and tubular body made of fiber-reinforced epoxy resin material |
| JP2014111726A (en) * | 2012-10-31 | 2014-06-19 | Dunlop Sports Co Ltd | Prepreg, fiber-reinforced epoxy resin molded product and tubular body made of fiber-reinforced epoxy resin material |
| JP2014111727A (en) * | 2012-10-31 | 2014-06-19 | Dunlop Sports Co Ltd | Fiber-reinforced epoxy resin material and tubular body made of the same |
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1995
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007088889A1 (en) | 2006-02-03 | 2007-08-09 | Asahi Kasei Chemicals Corporation | Microcapsule type hardener for epoxy resin, masterbatch type hardener composition for epoxy resin, one-pack type epoxy resin composition, and processed article |
| US7927514B2 (en) | 2006-02-03 | 2011-04-19 | Asahi Kasei Chemicals Corporation | Microcapsule-based hardener for epoxy resin, masterbatch-based hardener composition for epoxy resin, one-part epoxy resin composition, and processed good |
| JP2010001403A (en) * | 2008-06-20 | 2010-01-07 | Taiyo Ink Mfg Ltd | Thermosetting resin composition |
| CN103183932A (en) * | 2011-12-29 | 2013-07-03 | 邓禄普体育用品株式会社 | Tubular body made of fiber-reinforced epoxy resin material |
| JP2013139511A (en) * | 2011-12-29 | 2013-07-18 | Dunlop Sports Co Ltd | Tubular body made of fiber-reinforced epoxy resin material |
| WO2014021386A1 (en) | 2012-07-31 | 2014-02-06 | 旭化成イーマテリアルズ株式会社 | Epoxy resin composition, epoxy resin, and cured article |
| WO2014069576A1 (en) * | 2012-10-31 | 2014-05-08 | ダンロップスポーツ株式会社 | Fiber-reinforced epoxy resin material, prepreg, and tubular body made of fiber-reinforced epoxy resin material |
| JP2014111726A (en) * | 2012-10-31 | 2014-06-19 | Dunlop Sports Co Ltd | Prepreg, fiber-reinforced epoxy resin molded product and tubular body made of fiber-reinforced epoxy resin material |
| JP2014111727A (en) * | 2012-10-31 | 2014-06-19 | Dunlop Sports Co Ltd | Fiber-reinforced epoxy resin material and tubular body made of the same |
| US20150290900A1 (en) * | 2012-10-31 | 2015-10-15 | Dunlop Sports Co., Ltd. | Fiber-reinforced epoxy resin material, prepreg and, tubular body made of fiber-reinforced epoxy resin material |
| US9840058B2 (en) | 2012-10-31 | 2017-12-12 | Dunlop Sports Co. Ltd. | Fiber-reinforced epoxy resin material, prepreg and, tubular body made of fiber-reinforced epoxy resin material |
| WO2018169059A1 (en) | 2017-03-17 | 2018-09-20 | 旭化成株式会社 | Thermosetting resin composition |
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