JP3958471B2 - Epoxy resin composition for self-adhesive surface material and prepreg - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、航空機用ハニカムサンドイッチパネルの表面材用プリプレグに適した樹脂組成物及びこの樹脂組成物をマトリックス樹脂とした、航空機用ハニカムサンドイッチパネルの表面材用プリプレグに関する。
【０００２】
更に詳しくは、航空機用ハニカムサンドイッチパネルの表面材用自己接着性プリプレグに関する。
【０００３】
【従来の技術】
従来、芯材となるハニカムの両面に、表面材を貼り付けた、いわゆるハニカムサンドイッチパネルは、軽量構造材として広く使用されている。
【０００４】
表面材としては金属や各種繊維を強化材とした複合材料の板材が使用されている。特に、表面材として炭素繊維を強化材繊維とした樹脂複合材料を使用したハニカムサンドイッチパネルは航空機の二次構造材から一次構造材にまで使用範囲が拡大している。
【０００５】
一般に繊維強化樹脂複合材を使用したハニカムサンドイッチパネルの製造においては、▲１▼表面材となる複合材料を予め成形した後、該表面材をフィルム状接着剤を用いてハニカム芯材に接着する方法と、▲２▼ハニカム芯材に、表面材となるプリプレグを積層して、該プリプレグの硬化とハニカム芯材への接着とを同時に行う方法、いわゆるコキュア成形法とがある。
【０００６】
この内、後者▲２▼の方法は、一工程でハニカムサンドイッチパネルが成形できる為、工程数が少なく、製造コストを低減できるという利点がある。
【０００７】
また、上述のコキュア成形法には、更に、▲３▼ハニカム芯材とプリプレグとの間にフィルム状接着剤を介在させてプリプレグの成形硬化と同時に両者を接着させる方法（フィルム状接着剤法）と、▲４▼プリプレグに含まれるマトリックス樹脂そのものがハニカム芯材との接着剤として働く、いわゆる自己接着性を有するプリプレグを使用して、フィルム状接着剤を使わずに成形する方法（自己接着性プリプレグ法）、とに二分される。
【０００８】
特に航空機のような分野に使用されるハニカムサンドイッチパネルでは、自己接着性を有するプリプレグを使用する方法が、フィルム状接着剤を使用しないので、軽量化効果の点で望まれており、該方法は工程簡素化効果もある。
【０００９】
更に、航空機用材料にあっては、耐熱性の要求が高く、具体的には樹脂硬化物のガラス転移温度Ｔｇで示される耐熱性が１８０℃前後のものが、航空機用一次構造材として望まれている。
【００１０】
一般に高いＴｇの樹脂組成物は硬化温度が高く、このような樹脂組成物は、硬化時の揮発分が多い傾向にある。硬化時に揮発分が多いと、表面材形成時にハニカムの中にガス化した揮発分が封入され、出口のないハニカムの中で膨張し、表面材とハニカム芯材とを引き離すため、いわゆるフィレット形成を阻害し、且つ表面材とハニカム芯材との接着を阻害する要因となる。
【００１１】
ハニカム芯材と表面材との良好な接着性を得るためには、表面材とハニカム芯材との間に形成される樹脂垂れ、即ち、フィレットの形成性が重要であるといわれている。フィレットが小さい、或いは大きくても部分的に欠損が存在するようなフィレット形成性が悪い場合、表面材とハニカム芯材との接着性が不充分となり、ハニカムサンドイッチパネルの表面材とハニカム芯材との接着を阻害する要因となる。
【００１２】
ハニカム芯材と表面材との良好な接着性が得られなければ、機械特性、例えば、フラットワイズ引張強度で代表される特性が低下するという問題を生ずる。
【００１３】
上記▲４▼に示した自己接着性を有するプリプレグを使用する方法においては、硬化に際しマトリックス樹脂が垂れすぎると、ハニカムサンドイッチパネルの上下の表面材の接着部において、下部接着部はフィレットは大きくなるが、上部接着部のフィレットは形成されないか或いは小さなものとなる。
【００１４】
一方、マトリックス樹脂の垂れを少なくすると、やはりフィレットは小さなものとなる。従って、フィレットの形成性を良好なものとするためには、マトリックス樹脂の垂れ具合を、ある適正な範囲にコントロールする必要がある。
【００１５】
マトリックス樹脂の垂れを制御する一つの方法として、アエロジル（商品名、日本アエロジル株式会社製）に代表される揺変性を有する成分を添加することは最も簡便な方法として公知であるが、これを自己接着性プリプレグに適用した場合、樹脂基材自体の粘度は変化しないため、成形時にハニカム内圧により、プリプレグのハニカム側（内側）表面の樹脂はプリプレグ内に押し戻され、ハニカムにフィレットを形成しない場合があり好ましくない。
【００１６】
従来、樹脂の粘度調整に対しては、いくつかの解決策が講じられている。
例えば、特開平９−１３２６３６号公報にはマトリックス樹脂にジシクロペンタジエン骨格を有するエポキシ樹脂とグリシジルアミノ基を有するエポキシ樹脂を含有させ、更にイミダゾール系硬化促進剤の特定量を添加することで、硬化に際し粘度を１０〜１０００ｐｏｉｓｅ、特に７０〜３００ｐｏｉｓｅに制御し、これによりハニカム成形性が向上したことが記載されている。
【００１７】
また、特開平９−１４３２４９号公報にはジシクロペンタジエン骨格を有するエポキシ樹脂、グリシジルアミノ基を有するエポキシ樹脂、芳香族アミン及び硬化促進剤を含む樹脂組成物に、カルボキシ変性アクリロニトリルブタジエンゴム及び／またはカルボキシ変性（水素化）アクリロニトリルブタジエンゴムを特定量含有せしめ、更に硬化促進剤を添加することで、硬化に際し粘度を１０〜１０００ｐｏｉｓｅ、特に７０〜３００ｐｏｉｓｅに調整し、これにより良好なハニカム成形性が得られたと記載されている。
これらの方法では、少量の硬化剤成分の使用でエポキシ樹脂組成物の粘度調整を行うため、粘度調整のコントロールがし難いという問題点がある。
【００１８】
【発明が解決しようとする課題】
本発明は、樹脂組成物の揮発成分を少なく、しかも耐熱性を高くし、このような性質を有する樹脂組成物を使用して良好なる接着性を有する自己接着ハニカムサンドイッチパネルの表面材用のエポキシ樹脂組成物及び該エポキシ樹脂組成物を用いたプリプレグを提供することを目的とする。
【００１９】
更に本発明は、マトリックス樹脂自体の硬化時粘度を制御し、均一なフィレットを形成させることにより、高い機械特性、例えば、高いフラットワイズ引張強度をハニカムサンドイッチパネルに与えることができるエポキシ樹脂組成物を提供すること、及び該エポキシ樹脂組成物を用いたプリプレグを提供することを目的とする。
【００２０】
【課題を解決するための手段】
本発明の自己接着性表面材用エポキシ樹脂組成物は、１８０℃における揮発分が０．０３〜１．３５重量％であり、且つ硬化時最低粘度が８〜２０ｐｏｉｓｅのエポキシ樹脂組成物であり、該エポキシ樹脂組成物が下記の［Ａ］〜［Ｅ］の成分を含む自己接着性表面材用エポキシ樹脂組成物であることを特徴とする。
［Ａ］グリシジルアミノ基を有する多官能エポキシ樹脂
［Ｂ］［Ａ］以外のエポキシ樹脂
［Ｃ］ポリイソシアネート
［Ｄ］熱可塑性樹脂
［Ｅ］芳香族アミン系硬化剤
【００２１】
また、本発明のプリプレグは、このような自己接着性表面材用エポキシ樹脂組成物を繊維強化材シートに含浸させてなることを特徴とする。本発明のプリプレグは、フィレット形成性が良いので、表面材としての該プリプレグを、ハニカムコア（ハニカム芯材）に対して該ハニカム芯材の断面を接合面として接着させた場合には、ハニカム芯材と良好に接着し、得られたハニカムサンドイッチパネルは、機械特性、例えば、フラットワイズ引張強度で代表される特性が向上する。
本発明において使用する用語「硬化時最低粘度」中の「硬化時」とは、ある温度スケジュールに沿って加熱し、硬化させる過程を意味する。
【００２２】
【発明の実施の形態】
本発明のプリプレグは、繊維集合体に該自己接着性表面材用エポキシ樹脂組成物を３０〜５０重量％含浸させることによって得られる。
【００２３】
［Ａ］グリシジルアミノ基を有する多官能エポキシ樹脂
［Ｂ］［Ａ］以外のエポキシ樹脂
［Ｃ］ポリイソシアネート
［Ｄ］熱可塑性樹脂
［Ｅ］芳香族アミン系硬化剤
このような樹脂組成物を含む、本発明のプリプレグは、繊維集合体に該樹脂を３０〜５０重量％含浸させることによって得られる。
【００２４】
マトリックス樹脂としての本発明の自己接着性表面材用エポキシ樹脂組成物の製造時に、［Ｃ］成分を［Ａ］成分と、［Ｃ］成分を［Ｂ］成分と、又は［Ｃ］成分を［Ａ］成分と［Ｂ］成分の両方の成分と予備反応させることにより、樹脂組成物全体が架橋構造となり、粘度が上昇する。このような樹脂組成物をマトリックス樹脂としたプリプレグは、フィレットの形成性が向上する。したがって、該樹脂組成物を用いたプリプレグからなる表面材と、ハニカム芯材とにより、ハニカムサンドイッチパネルを成形すると、表面材とハニカム芯材との接着性が高まり、成形されたハニカムサンドイッチパネルは、ハニカム芯材と表面材との良好な接着状態となり、機械特性、例えば、フラットワイズ引張強度で代表される特性が向上する。
【００２５】
本発明の自己接着性表面材用エポキシ樹脂組成物の構成成分［Ａ］〜［Ｅ］成分について更に説明する。
【００２６】
［Ａ］グリシジルアミノ基を有する多官能エポキシ樹脂：
本発明のエポキシ樹脂組成物に用いられるグリシジルアミノ基を有する多官能エポキシ樹脂成分［Ａ］としては、Ｎ，Ｎ，Ｎ，Ｎ−テトラグリシジルジアミノジフェニルメタン〔市販品として油化シェルエポキシ社製Ｅｐｉｋｏｔｅ６０４（商品名）、住友化学社製スミエポキシＥＬＭ−４３４（商品名）、旭チバ社製Ａｒａｌｄｉｔｅ ＭＹ９６３４（商品名）など〕、Ｎ，Ｎ，Ｏ−トリグリシジル−ｐ−アミノフェノール（市販品として住友化学社製スミエポキシＥＬＭ−１００（商品名）など）等が挙げられる。本発明において多官能エポキシ樹脂とは３個以上のエポキシ基を持つエポキシ樹脂をいう。これらの多官能エポキシ樹脂は硬化物に高い耐熱性を与える。
【００２７】
該エポキシ樹脂の全エポキシ樹脂に対する配合量は３０〜７０重量％含有するのが耐熱性を高め、且つ靭性を維持する上で好ましい。Ａ成分比が３０％未満だと耐熱性が低くなる。一方、Ａ成分比が７０％を越えると硬化物が脆性化し、靱性が低下し耐衝撃性が低下する。
【００２８】
［Ｂ］その他のエポキシ樹脂
本発明のエポキシ樹脂組成物に用いられるその他のエポキシ樹脂成分［Ｂ］としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂などの２官能エポキシ樹脂、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などのノボラック型エポキシ樹脂等の多官能エポキシ樹脂等が挙げられる。更に、ウレタン変性エポキシ樹脂、ゴム変性エポキシ樹脂などの各種変性エポキシ樹脂も用いることができる。
【００２９】
これらの樹脂を適時選択して１種あるいは２種以上を混合して用いることができる。この中で、ビスフェノール型に代表される２官能エポキシ樹脂は分子量の違いにより液状から固形まで種々のグレードがあり、プリプレグ用マトリックス樹脂に配合する場合、適宜これらを混合して粘度調整を行うことが可能である。
【００３０】
［Ｃ] ポリイソシアネート
本発明のエポキシ樹脂組成物に用いられるポリイソシアネート成分［Ｃ］としては、エポキシ樹脂と反応して増粘効果があるものであれば特に限定される物ではない。［Ｃ］成分の配合量は全エポキシ樹脂に対し２〜７重量％用いるのが好ましく、この範囲より多すぎるとプリプレグのタック性及びドレープ性が低下するので、プリプレグの取扱性が損なわれ、更に硬化物の靭性低下を招く。一方、この範囲より少なすぎると増粘効果が小さくハニカムサンドイッチパネルを成形した場合、マトリックス樹脂が垂れすぎるためフィレットの形成性が低下する。
【００３１】
［Ｃ］成分は、［Ａ］成分又は［Ｂ］成分又はこれらの両成分と予備反応させて使用するのがよい。予備反応をさせないと、樹脂組成物の吸湿性が高くなり、プリプレグの製造時、保管時及び使用時に吸湿し性能低下の原因となる。また樹脂の粘度低下がありフィレット形成能が低下する。
【００３２】
［Ｄ］熱可塑性樹脂
熱可塑性樹脂を本発明のエポキシ樹脂組成物に含ませることにより、エポキシ樹脂組成物の硬化物の耐衝撃性を向上させることができ、しかも耐熱性を殆ど低下させない。特に、エポキシ樹脂に可溶な熱可塑性樹脂は、前記特性に加えて、熱可塑性樹脂の硬化過程でエポキシ樹脂に溶解し、マトリックスの粘度を増加させ、エポキシ樹脂組成物の粘度の低下を防ぐ効果がある。図１に、エポキシ樹脂に熱可塑性樹脂を添加した場合と、添加しない場合において、樹脂組成物の種々の温度に対する粘度の関係の傾向を表したグラフを示す。
【００３３】
本発明のエポキシ樹脂組成物に用いられる熱可塑性樹脂成分［Ｄ］としてはポリエーテルスルホン（ＰＥＳ）、ポリエーテルイミド（ＰＥＩ）に代表される熱可塑性樹脂のほか、カルボキシ末端スチレンブタジエンゴム、カルボキシ末端水素化アクリロニトリルブタジエンゴムに代表されるゴム成分が挙げられる。
【００３４】
これらの熱可塑性樹脂は、エポキシ樹脂（［Ａ］成分、［Ｂ］成分）に溶解又は分散させ、又はこれらの併用によって用いられる。全エポキシ樹脂１００重量％に対して、熱可塑性樹脂は５〜５０重量％、好ましくは１０〜３０重量％配合させることが適当である。
【００３５】
［Ｅ］芳香族アミン系硬化剤
芳香族アミン系硬化剤を本発明のエポキシ樹脂組成物に含ませることにより、エポキシ樹脂組成物の硬化物に高い耐熱性を発現させることができる。本発明のエポキシ樹脂組成物に用いられる芳香族アミン系硬化剤成分［Ｅ］としてはジアミノジフェニルスルホン（ＤＤＳ）、ジアミノジフェニルメタン（ＤＤＭ）等、エポキシ樹脂の硬化剤として用いられるものであり、１８０℃硬化に対応できるものであれば特に限定されるものではない。これらは単独で、あるいは２種以上の混合物として使用しても良いが、耐熱性を付与する点でＤＤＳの誘導体が好ましい。
【００３６】
本発明の樹脂組成物は、上述した［Ａ］［Ｂ］［Ｃ］［Ｄ］及び［Ｅ］成分を必須とするものであるが、本発明の効果を損なわない範囲で、必要に応じて上述以外の硬化剤、熱硬化性樹脂、充填剤、老化防止剤、難燃剤、顔料等の各種添加剤を含有していてもよい。
【００３７】
プリプレグの製造
プリプレグの製造方法としては本発明のエポキシ樹脂組成物を離型紙の上に薄いフィルム状に塗布し、剥離して得られた樹脂フィルムを、強化繊維シートに積層成形してエポキシ樹脂組成物を含浸させるホットメルト法や、エポキシ樹脂組成物を適当な溶媒を用いてワニス状にし、このワニスを強化繊維に含浸させる溶剤法が挙げられる。
【００３８】
本発明のプリプレグに使用できる強化繊維としては炭素繊維、黒鉛繊維、アラミド繊維、ガラス繊維等を用いることができる。これらの強化繊維は一方向、或いは織物状の形態で使用することができる。本発明のプリプレグはハニカムサンドイッチパネル成形用の自己接着性プリプレグである。プリプレグに含まれるマトリックス樹脂自身がハニカム芯材との接着に使用される際に、フィレットの形成性を良好にするために、プリプレグ中の樹脂含有率は通常のプリプレグよりやや高い、３０〜５０重量％とするのが好ましい。
【００３９】
【実施例】
以下、実施例により本発明を更に詳細に説明する。
本実施例、比較例において樹脂組成物の各種試験方法は下記にしたがって行った。
【００４０】
（１）硬化時最低粘度
各樹脂組成物の粘度は、レオロジ社製ＭＲ−５００型ソリキッドメーターにより、直径４０ｍｍのパラレルプレートを用い、昇温速度２℃／分、周波数１Ｈｚ、プレートギャップ０．５ｍｍの条件で測定した。
【００４１】
（２）ガラス転移点［Ｔｇ］
各樹脂組成物を１８０℃で２時間硬化させた。得られた硬化物のＴｇをＴＭＡによるペネトレーション法にて１０℃／分の昇温速度、且つ直径１ｍｍの検出棒に２０ｇの荷重を掛けて測定した。
【００４２】
（３）フィレット形成性
エポキシ樹脂組成物をホットメルト法にて炭素繊維〔東邦レーヨン社製ＨＴＡ−１２Ｋ（商品名）：１２０００フィラメント〕に含浸せしめ、繊維目付１４５ｇ／ｍ2 、樹脂含有率３７重量％の一方向プリプレグ（ＵＤプリプレグ）を作製した。このようにして作製したプリプレグを、昭和飛行機社製ノーメックスハニカム芯材（セルサイズ３／１６インチ）の上下面にフィルム接着剤を介さずに貼合せ、オートクレーブにて昇温速度２℃／分、圧力２ｋｇｆ／ｃｍ2 で１８０℃まで昇温し、その後１８０℃に２時間保った。
【００４３】
かくして得られたハニカムサンドイッチパネルをハニカム面に対し垂直に切断し、ハニカム芯材の上下両端に欠損が無く、且つ各部分に対し３００μｍ以上の均一なフィレットが形成されている場合は「○」、フィレットが形成されていないか欠損を生じている場合を「×」として判定した。
【００４４】
（４）揮発分
上記（３）で作製したプリプレグを１００ｍｍ×１００ｍｍに裁断し、試験片とする。該試験片を秤量後（Ｗ1 ）、１８０℃に設定した恒温槽内にアルミニウム板に載せたプリプレグを静置した状態で２時間維持し、デシケーター中で室温まで放冷し、試験片を秤量した（Ｗ2 ）。次式より揮発分（重量％）を計算した。
【００４５】
ＰＶＣ＝ （Ｗ1 −Ｗ2 ）×１００／Ｗ1
ＰＶＣ：プリプレグの揮発分 （重量％）
揮発分（重量）％＝ＰＶＣ×１００／ＲＣ
ＲＣ：プリプレグの樹脂含有率（重量）％
【００４６】
（５）フラットワイズ引張強度
上記（３）で作製したハニカムサンドイッチパネルのフラットワイズ引張強度をＭＩＬ−ＳＴＤ−４０１Ｂ（米軍用規格）に従って評価した。
【００４７】
〔実施例１〜６〕
下記の表１に示す組成の［Ａ］成分及び［Ｂ］成分をニーダー中にて加熱・混合させた。得られた混合物中に［Ｃ］成分を添加し、更にニーダー中で加熱混合することにより、［Ｃ］成分と［Ａ］成分及び［Ｂ］成分と完全に反応させた。続いて、得られた樹脂混合物をロールミルに移し、［Ｄ］成分と［Ｅ］成分及びその他の成分とを良く混練し、本実施例１〜６のエポキシ樹脂組成物を得た。このエポキシ樹脂組成物の揮発分〔重量％〕と硬化時最低粘度を下記の表１に示す。また、本実施例１〜６のエポキシ樹脂組成物について、耐熱性、フィレット形成性、フラットワイズ引張強度について評価した結果を下記の表１に示す。
【００４８】
〔比較例１〕
下記の表１に示す組成の［Ｂ］成分と［Ｄ］成分とをニーダー中で加熱・溶解させた。この混合物に［Ａ］成分と［Ｃ］成分を加え、更にニーダー中で加熱混合することにより、［Ｃ］成分とエポキシ樹脂成分［Ａ］及び［Ｂ］とを完全に反応させた。続いて、得られた樹脂混合物をロールミルに移し、［Ｅ］成分及びその他の成分とを良く混練し、揮発分及び粘度の異なるエポキシ樹脂組成物を調製した。
このエポキシ樹脂組成物を、前記実施例と同様にして評価した結果を下記の表１に示す。
【００４９】
〔比較例２〕
下記の表１に示す組成の［Ｂ］成分と［Ｄ］成分とをニーダー中で加熱・溶解させた。この混合物をロールミルに移し、［Ａ］成分、［Ｅ］成分及びその他の成分とを良く混練し、揮発分及び粘度の異なるエポキシ樹脂組成物を調製した。得られた樹脂組成物を、実施例と同様にして評価した結果を下記の表１に示す。
【００５０】
〔比較例３〕
下記の表１に示す組成の［Ｂ］成分と［Ｄ］成分とをニーダー中で加熱・溶解させた。この混合物に［Ａ］成分と［Ｃ］成分を加え、更にニーダー中で加熱混合することにより、［Ｃ］成分とエポキシ樹脂成分［Ａ］及び［Ｂ］とを完全に反応させた。続いて、得られた本樹脂混合物をロールミルに移し、［Ｅ］成分とを良く混練し、エポキシ樹脂組成物を調製した。得られたエポキシ樹脂組成物を、前記実施例と同様にして評価した結果を下記の表１に示す。
【００５１】
〔比較例４〕
下記の表１に示す組成の［Ａ］、［Ｂ］、［Ｄ］、［Ｅ］及びその他の各成分とをロールミルにて良く混練し、樹脂組成物を調製した。得られたエポキシ樹脂組成物を、前記実施例と同様にして評価した結果を下記の表１に示す。
【００５２】
【表１】
【発明の効果】
本発明の自己接着性表面材用エポキシ樹脂組成物によれば、揮発分が０．０３〜１．３５重量％（１８０℃における）と低く、且つ硬化時最低粘度が８〜２０ｐｏｉｓｅと最適範囲であるためフィレットの形成性が高く、該エポキシ樹脂組成物を含浸してなるプリプレグを用いて成形したハニカムサンドイッチパネルはフラットワイズ引張強度に代表される機械特性が良好である。
【図面の簡単な説明】
【図１】エポキシ樹脂に熱可塑性樹脂を添加した場合と、添加しない場合において、樹脂組成物の種々の温度に対する粘度の関係の傾向を表したグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition suitable for an aircraft honeycomb sandwich panel surface material prepreg and an aircraft honeycomb sandwich panel surface material prepreg using the resin composition as a matrix resin.
[0002]
More particularly, the present invention relates to a self-adhesive prepreg for a surface material of an aircraft honeycomb sandwich panel.
[0003]
[Prior art]
Conventionally, so-called honeycomb sandwich panels in which surface materials are attached to both surfaces of a honeycomb serving as a core material have been widely used as lightweight structural materials.
[0004]
As the surface material, a composite material plate made of metal or various fibers is used. In particular, a honeycomb sandwich panel using a resin composite material in which carbon fibers are used as reinforcing material fibers as a surface material has been expanded in use from an aircraft secondary structure material to a primary structure material.
[0005]
In general, in the manufacture of a honeycomb sandwich panel using a fiber reinforced resin composite material, (1) a method of previously molding a composite material to be a surface material and then bonding the surface material to the honeycomb core material using a film adhesive And (2) a method of laminating a prepreg as a surface material on a honeycomb core material, and simultaneously curing the prepreg and adhering to the honeycomb core material, a so-called cocure molding method.
[0006]
Among these, the latter method (2) has the advantage that the number of steps can be reduced and the manufacturing cost can be reduced because the honeycomb sandwich panel can be formed in one step.
[0007]
Further, in the above-mentioned cocure molding method, (3) a method in which a film adhesive is interposed between the honeycomb core material and the prepreg, and the prepreg is molded and cured at the same time (film adhesive method). And (4) a method of molding without using a film adhesive (self-adhesiveness) using a prepreg having a so-called self-adhesive property in which the matrix resin itself contained in the prepreg acts as an adhesive with the honeycomb core material. Prepreg method).
[0008]
Particularly in honeycomb sandwich panels used in fields such as aircraft, a method of using a prepreg having self-adhesiveness is desired in terms of lightening effect because a film-like adhesive is not used. There is also a process simplification effect.
[0009]
Further, aircraft materials have a high demand for heat resistance. Specifically, a material having a heat resistance of about 180 ° C. indicated by a glass transition temperature Tg of a cured resin is desired as a primary structural material for aircraft. ing.
[0010]
In general, a resin composition having a high Tg has a high curing temperature, and such a resin composition tends to have a large amount of volatile components during curing. When there is a large amount of volatile matter during curing, the gasified volatile matter is enclosed in the honeycomb when forming the surface material, expands in the honeycomb without an outlet, and separates the surface material and the honeycomb core material, so-called fillet formation is performed. This is a factor that inhibits adhesion between the surface material and the honeycomb core material.
[0011]
In order to obtain good adhesion between the honeycomb core material and the surface core material, it is said that the resin dripping formed between the surface material and the honeycomb core material, that is, the fillet formability is important. When the fillet is small or large, but the fillet formation is poor, such as when there are defects, the adhesion between the surface material and the honeycomb core material becomes insufficient, and the surface material of the honeycomb sandwich panel and the honeycomb core material It becomes a factor that inhibits adhesion.
[0012]
If good adhesion between the honeycomb core material and the surface material is not obtained, there arises a problem that mechanical characteristics such as characteristics represented by flatwise tensile strength are deteriorated.
[0013]
In the method using the prepreg having self-adhesiveness shown in the above (4), if the matrix resin droops too much during curing, the fillet becomes large in the lower adhesive portion at the upper and lower surface material adhesive portions of the honeycomb sandwich panel. However, the fillet of the upper adhesive portion is not formed or becomes small.
[0014]
On the other hand, if the dripping of the matrix resin is reduced, the fillet becomes small. Therefore, in order to improve the fillet formation, it is necessary to control the sagging state of the matrix resin within a certain appropriate range.
[0015]
As one method for controlling the dripping of the matrix resin, it is known as the simplest method to add a thixotropic component represented by Aerosil (trade name, manufactured by Nippon Aerosil Co., Ltd.). When applied to an adhesive prepreg, the viscosity of the resin base material itself does not change, so the resin on the honeycomb side (inside) surface of the prepreg is pushed back into the prepreg during molding, and the fillet may not be formed in the honeycomb. There is not preferable.
[0016]
Conventionally, several solutions have been taken for resin viscosity adjustment.
For example, JP-A-9-132636 discloses that a matrix resin contains an epoxy resin having a dicyclopentadiene skeleton and an epoxy resin having a glycidylamino group, and is further cured by adding a specific amount of an imidazole curing accelerator. In this case, it is described that the viscosity is controlled to 10 to 1000 poise, particularly 70 to 300 poise, thereby improving the honeycomb formability.
[0017]
JP-A-9-143249 discloses a resin composition containing an epoxy resin having a dicyclopentadiene skeleton, an epoxy resin having a glycidylamino group, an aromatic amine and a curing accelerator, and a carboxy-modified acrylonitrile butadiene rubber and / or By adding a specific amount of carboxy-modified (hydrogenated) acrylonitrile butadiene rubber and further adding a curing accelerator, the viscosity is adjusted to 10 to 1000 poise, particularly 70 to 300 poise, and thereby good honeycomb formability is obtained. It is described that it was done.
In these methods, since the viscosity of the epoxy resin composition is adjusted by using a small amount of a curing agent component, there is a problem that it is difficult to control the viscosity adjustment.
[0018]
[Problems to be solved by the invention]
The present invention relates to an epoxy for a surface material of a self-adhesive honeycomb sandwich panel that has a low volatile component of a resin composition, has high heat resistance, and has good adhesion by using a resin composition having such properties. It aims at providing the prepreg using the resin composition and this epoxy resin composition.
[0019]
Furthermore, the present invention provides an epoxy resin composition capable of providing a honeycomb sandwich panel with high mechanical properties, for example, high flatwise tensile strength, by controlling the viscosity at the time of curing of the matrix resin itself and forming a uniform fillet. It aims at providing and the prepreg using this epoxy resin composition.
[0020]
[Means for Solving the Problems]
Self-adhesive surface material for the epoxy resin composition of the present invention is a volatile content from 0.03 to 1.35 wt% at 180 ° C., and is cured at the minimum viscosity Ri epoxy resin composition der of 8~20poise The epoxy resin composition is an epoxy resin composition for self-adhesive surface material containing the following components [A] to [E] .
[A] Multifunctional epoxy resin having glycidylamino group
[B] Epoxy resins other than [A]
[C] Polyisocyanate
[D] Thermoplastic resin
[E] Aromatic amine curing agent
Moreover, the prepreg of the present invention is characterized in that a fiber reinforcing material sheet is impregnated with such an epoxy resin composition for a self-adhesive surface material. Since the prepreg of the present invention has good fillet formability, when the prepreg as a surface material is bonded to the honeycomb core (honeycomb core material) with the cross section of the honeycomb core material as a bonding surface, the honeycomb core The honeycomb sandwich panel obtained by adhering well to the material has improved mechanical characteristics, for example, characteristics represented by flatwise tensile strength.
The term “during curing” in the term “minimum viscosity during curing” used in the present invention means a process of heating and curing according to a certain temperature schedule.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
The prepreg of the present invention is obtained by impregnating a fiber assembly with 30 to 50% by weight of the epoxy resin composition for self-adhesive surface material .
[0023]
[A] Polyfunctional epoxy resin having glycidylamino group [B] Epoxy resin other than [A] [C] Polyisocyanate [D] Thermoplastic resin [E] Aromatic amine-based curing agent Including such a resin composition The prepreg of the present invention is obtained by impregnating a fiber assembly with 30 to 50% by weight of the resin.
[0024]
When producing the epoxy resin composition for self-adhesive surface material of the present invention as a matrix resin, the [C] component is the [A] component, the [C] component is the [B] component, or the [C] component is [ By pre-reacting with both the A] component and the [B] component, the entire resin composition becomes a crosslinked structure, and the viscosity increases. A prepreg using such a resin composition as a matrix resin has improved fillet formation. Therefore, when a honeycomb sandwich panel is formed from a surface material made of a prepreg using the resin composition and a honeycomb core material, the adhesion between the surface material and the honeycomb core material is increased, and the formed honeycomb sandwich panel is A good bonding state between the honeycomb core material and the surface material is obtained, and mechanical characteristics, for example, characteristics represented by flatwise tensile strength are improved.
[0025]
The components [A] to [E] of the epoxy resin composition for a self-adhesive surface material of the present invention will be further described.
[0026]
[A] Multifunctional epoxy resin having a glycidylamino group:
As the polyfunctional epoxy resin component [A] having a glycidylamino group used in the epoxy resin composition of the present invention, N, N, N, N-tetraglycidyldiaminodiphenylmethane [Epikote 604 manufactured by Yuka Shell Epoxy as a commercial product ( Product name), Sumitomo Chemical Co., Ltd. Sumiepoxy ELM-434 (product name), Asahi Ciba Araldite MY9634 (product name), etc.], N, N, O-triglycidyl-p-aminophenol (commercially available as Sumitomo Chemical Co., Ltd.) Sumiepoxy ELM-100 (trade name), etc.). In the present invention, the polyfunctional epoxy resin refers to an epoxy resin having three or more epoxy groups. These polyfunctional epoxy resins impart high heat resistance to the cured product.
[0027]
The blending amount of the epoxy resin with respect to the total epoxy resin is preferably 30 to 70% by weight from the viewpoint of improving heat resistance and maintaining toughness. When the A component ratio is less than 30%, the heat resistance is lowered. On the other hand, if the A component ratio exceeds 70%, the cured product becomes brittle, the toughness is lowered, and the impact resistance is lowered.
[0028]
[B] Other Epoxy Resins Other epoxy resin components [B] used in the epoxy resin composition of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy. Examples thereof include a bifunctional epoxy resin such as a resin, a polyfunctional epoxy resin such as a novolac epoxy resin such as a phenol novolac epoxy resin and a cresol novolac epoxy resin. Furthermore, various modified epoxy resins such as urethane-modified epoxy resin and rubber-modified epoxy resin can also be used.
[0029]
These resins can be selected as appropriate and used alone or in combination of two or more. Among these, bifunctional epoxy resins represented by the bisphenol type have various grades ranging from liquid to solid depending on the difference in molecular weight. When blended in a matrix resin for prepreg, the viscosity can be adjusted by mixing them appropriately. Is possible.
[0030]
[C] Polyisocyanate The polyisocyanate component [C] used in the epoxy resin composition of the present invention is not particularly limited as long as it has a thickening effect by reacting with the epoxy resin. The blending amount of the component [C] is preferably 2 to 7% by weight based on the total epoxy resin, and if it is more than this range, the prepreg tackiness and draping properties are reduced, so that the prepreg handling property is impaired. The toughness of the cured product is reduced. On the other hand, if the content is less than this range, the thickening effect is small, and when a honeycomb sandwich panel is formed, the matrix resin droops too much and fillet formation is reduced.
[0031]
The [C] component is preferably used after being pre-reacted with the [A] component, the [B] component, or both of these components. If the preliminary reaction is not carried out, the hygroscopicity of the resin composition becomes high, and the hygroscopic property is absorbed during production, storage and use of the prepreg, resulting in a decrease in performance. In addition, the viscosity of the resin is lowered and the fillet forming ability is lowered.
[0032]
[D] Thermoplastic resin By including the thermoplastic resin in the epoxy resin composition of the present invention, the impact resistance of the cured product of the epoxy resin composition can be improved, and the heat resistance is hardly lowered. In particular, the thermoplastic resin soluble in the epoxy resin has the effect of preventing the lowering of the viscosity of the epoxy resin composition by dissolving in the epoxy resin during the curing process of the thermoplastic resin, increasing the viscosity of the matrix, in addition to the above properties. There is. In FIG. 1, the graph showing the tendency of the relationship of the viscosity with respect to the various temperature of a resin composition in the case where a thermoplastic resin is added to an epoxy resin, and the case where it does not add is shown.
[0033]
The thermoplastic resin component [D] used in the epoxy resin composition of the present invention includes a thermoplastic resin represented by polyethersulfone (PES) and polyetherimide (PEI), a carboxy-terminated styrene-butadiene rubber, and a carboxy-terminated terminal. The rubber component represented by hydrogenated acrylonitrile butadiene rubber is mentioned.
[0034]
These thermoplastic resins are dissolved or dispersed in an epoxy resin ([A] component, [B] component), or are used in combination. It is appropriate to add 5 to 50% by weight, preferably 10 to 30% by weight of the thermoplastic resin with respect to 100% by weight of the total epoxy resin.
[0035]
[E] Aromatic amine curing agent By containing an aromatic amine curing agent in the epoxy resin composition of the present invention, the cured product of the epoxy resin composition can exhibit high heat resistance. The aromatic amine-based curing agent component [E] used in the epoxy resin composition of the present invention is used as a curing agent for epoxy resins such as diaminodiphenyl sulfone (DDS) and diaminodiphenylmethane (DDM), and is 180 ° C. There is no particular limitation as long as it can cope with curing. These may be used alone or as a mixture of two or more, but a DDS derivative is preferred in terms of imparting heat resistance.
[0036]
The resin composition of the present invention essentially comprises the above-described components [A], [B], [C], [D], and [E], but as necessary, as long as the effects of the present invention are not impaired. Various additives such as curing agents other than those described above, thermosetting resins, fillers, anti-aging agents, flame retardants, and pigments may be contained.
[0037]
Production of prepreg As a method for producing prepreg, a resin film obtained by applying the epoxy resin composition of the present invention on a release paper as a thin film and peeling it is laminated and formed on a reinforcing fiber sheet. Examples thereof include a hot melt method in which the epoxy resin composition is impregnated and a solvent method in which the epoxy resin composition is made into a varnish using an appropriate solvent and the varnish is impregnated into the reinforcing fiber.
[0038]
Carbon fibers, graphite fibers, aramid fibers, glass fibers and the like can be used as reinforcing fibers that can be used in the prepreg of the present invention. These reinforcing fibers can be used in a unidirectional or woven form. The prepreg of the present invention is a self-adhesive prepreg for forming a honeycomb sandwich panel. When the matrix resin contained in the prepreg itself is used for bonding to the honeycomb core material, the resin content in the prepreg is slightly higher than that of a normal prepreg, in order to improve the fillet formation, 30 to 50 weight % Is preferable.
[0039]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
In the examples and comparative examples, various test methods for resin compositions were performed as follows.
[0040]
(1) Minimum viscosity upon curing The viscosity of each resin composition was measured using a parallel plate having a diameter of 40 mm, a temperature rise rate of 2 ° C./min, a frequency of 1 Hz, a plate gap of 0. Measurement was performed under the condition of 5 mm.
[0041]
(2) Glass transition point [Tg]
Each resin composition was cured at 180 ° C. for 2 hours. The Tg of the obtained cured product was measured by a TMA penetration method with a heating rate of 10 ° C./min and a detection rod having a diameter of 1 mm applied with a load of 20 g.
[0042]
(3) Carbon fiber [HTA-12K (trade name): 12000 filament manufactured by Toho Rayon Co., Ltd.] is impregnated with the fillet-forming epoxy resin composition by a hot melt method, the fiber basis weight is 145 g / m 2 , and the resin content is 37 weights. % Unidirectional prepreg (UD prepreg). The prepreg produced in this way was bonded to the upper and lower surfaces of Nomex honeycomb core material (cell size 3/16 inch) manufactured by Showa Aircraft Co., Ltd. without using a film adhesive, and the heating rate was 2 ° C./min in an autoclave. The temperature was raised to 180 ° C. at a pressure of 2 kgf / cm 2 , and then kept at 180 ° C. for 2 hours.
[0043]
When the honeycomb sandwich panel thus obtained is cut perpendicularly to the honeycomb surface, there is no defect on the upper and lower ends of the honeycomb core material, and a uniform fillet of 300 μm or more is formed for each part, `` O '', The case where a fillet was not formed or a defect occurred was determined as “x”.
[0044]
(4) Volatile content The prepreg produced in (3) above is cut into 100 mm × 100 mm to obtain test pieces. After weighing the test piece (W 1 ), the prepreg placed on the aluminum plate was left standing in a thermostat set at 180 ° C. for 2 hours, allowed to cool to room temperature in a desiccator, and the test piece was weighed. (W 2 ). The volatile content (% by weight) was calculated from the following formula.
[0045]
PVC = (W 1 −W 2 ) × 100 / W 1
PVC: Volatile content of prepreg (% by weight)
Volatile content (weight)% = PVC × 100 / RC
RC: Resin content (weight)% of prepreg
[0046]
(5) Flatwise tensile strength The flatwise tensile strength of the honeycomb sandwich panel produced in (3) above was evaluated according to MIL-STD-401B (US military standard).
[0047]
[Examples 1 to 6]
[A] component and [B] component of the composition shown in following Table 1 were heated and mixed in the kneader. The [C] component was added to the resulting mixture, and further heated and mixed in a kneader to completely react the [C] component, the [A] component, and the [B] component. Subsequently, the obtained resin mixture was transferred to a roll mill, and the [D] component, the [E] component and other components were well kneaded to obtain the epoxy resin compositions of Examples 1 to 6. Table 1 below shows the volatile content (% by weight) of the epoxy resin composition and the minimum viscosity upon curing. Table 1 below shows the results of evaluating the heat resistance, fillet-forming property, and flatwise tensile strength of the epoxy resin compositions of Examples 1 to 6.
[0048]
[Comparative Example 1]
[B] component and [D] component of the composition shown in the following Table 1 were heated and dissolved in a kneader. The [A] component and the [C] component were added to this mixture, and the mixture was further heated and mixed in a kneader to completely react the [C] component with the epoxy resin components [A] and [B]. Subsequently, the obtained resin mixture was transferred to a roll mill, and the [E] component and other components were well kneaded to prepare epoxy resin compositions having different volatile content and viscosity.
The results of evaluating this epoxy resin composition in the same manner as in the above Examples are shown in Table 1 below.
[0049]
[Comparative Example 2]
[B] component and [D] component of the composition shown in the following Table 1 were heated and dissolved in a kneader. This mixture was transferred to a roll mill, and the [A] component, [E] component and other components were well kneaded to prepare epoxy resin compositions having different volatile content and viscosity. The results of evaluating the obtained resin composition in the same manner as in Examples are shown in Table 1 below.
[0050]
[Comparative Example 3]
[B] component and [D] component of the composition shown in the following Table 1 were heated and dissolved in a kneader. The [A] component and the [C] component were added to this mixture, and the mixture was further heated and mixed in a kneader to completely react the [C] component with the epoxy resin components [A] and [B]. Subsequently, the obtained resin mixture was transferred to a roll mill, and the [E] component was well kneaded to prepare an epoxy resin composition. The results of evaluating the obtained epoxy resin composition in the same manner as in the above Examples are shown in Table 1 below.
[0051]
[Comparative Example 4]
[A], [B], [D], [E] and other components having the compositions shown in Table 1 below were well kneaded with a roll mill to prepare a resin composition. The results of evaluating the obtained epoxy resin composition in the same manner as in the above Examples are shown in Table 1 below.
[0052]
[Table 1]
【The invention's effect】
According to the epoxy resin composition for a self-adhesive surface material of the present invention, the volatile content is as low as 0.03 to 1.35% by weight (at 180 ° C.), and the minimum viscosity upon curing is 8 to 20 poise in the optimum range. Therefore, the fillet formability is high, and the honeycomb sandwich panel formed using the prepreg impregnated with the epoxy resin composition has good mechanical properties represented by flatwise tensile strength.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph showing the tendency of the relationship of viscosity to various temperatures of a resin composition when a thermoplastic resin is added to an epoxy resin and when a thermoplastic resin is not added.
Claims (7)
該エポキシ樹脂組成物が下記の成分を含む自己接着性表面材用エポキシ樹脂組成物。
［Ａ］グリシジルアミノ基を有する多官能エポキシ樹脂
［Ｂ］［Ａ］以外のエポキシ樹脂
［Ｃ］ポリイソシアネート
［Ｄ］熱可塑性樹脂
［Ｅ］芳香族アミン系硬化剤 A volatile content from 0.03 to 1.35 wt% at 180 ° C., and is cured at the minimum viscosity Ri epoxy resin composition der of 8～20Poise,
An epoxy resin composition for a self-adhesive surface material, wherein the epoxy resin composition comprises the following components.
[A] Multifunctional epoxy resin having glycidylamino group
[B] Epoxy resins other than [A]
[C] Polyisocyanate
[D] Thermoplastic resin
[E] Aromatic amine curing agent
［Ａ］グリシジルアミノ基を有する多官能エポキシ樹脂[A] Multifunctional epoxy resin having glycidylamino group
［Ｂ］［Ａ］以外のエポキシ樹脂[B] Epoxy resins other than [A]
［Ｃ］ポリイソシアネート[C] Polyisocyanate
［Ｄ］熱可塑性樹脂[D] Thermoplastic resin
［Ｅ］芳香族アミン系硬化剤[E] Aromatic amine curing agent
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| JP20734399A JP3958471B2 (en) | 1999-07-22 | 1999-07-22 | Epoxy resin composition for self-adhesive surface material and prepreg |
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| JP20734399A JP3958471B2 (en) | 1999-07-22 | 1999-07-22 | Epoxy resin composition for self-adhesive surface material and prepreg |
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| JP3958471B2 true JP3958471B2 (en) | 2007-08-15 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2439361C (en) * | 2001-02-27 | 2011-10-18 | Hexcel Corporation | Adhesive prepreg face sheets for sandwich panels |
| JP2004346092A (en) * | 2003-04-28 | 2004-12-09 | Yokohama Rubber Co Ltd:The | Resin composition for prepreg |
| CN1954024A (en) * | 2004-05-14 | 2007-04-25 | Cytec技术有限公司 | Self-adhesive prepreg |
| JP4802519B2 (en) * | 2005-03-07 | 2011-10-26 | 横浜ゴム株式会社 | Process for producing resin composition for self-adhesive prepreg |
| JP4972865B2 (en) * | 2005-03-09 | 2012-07-11 | 横浜ゴム株式会社 | Process for producing resin composition for self-adhesive prepreg |
| JP4972864B2 (en) * | 2005-03-09 | 2012-07-11 | 横浜ゴム株式会社 | Process for producing resin composition for self-adhesive prepreg |
| WO2009157295A1 (en) | 2008-06-25 | 2009-12-30 | 東邦テナックス株式会社 | Epoxy resin composition and prepreg using same |
| US8263216B2 (en) | 2009-03-24 | 2012-09-11 | Toray Industries, Inc. | Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
| WO2011037144A1 (en) | 2009-09-25 | 2011-03-31 | 横浜ゴム株式会社 | Thermosetting resin composition, thermosetting resin composition for fiber-reinforced composite material, prepreg using the same, and honeycomb sandwich panel |
| CA2810710A1 (en) | 2010-09-24 | 2012-03-29 | Toray Industries, Inc. | Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
| KR101532195B1 (en) | 2012-07-25 | 2015-06-26 | 도레이 카부시키가이샤 | Prepreg and carbon-fiber-reinforced composite material |
| CN104927310B (en) * | 2014-03-17 | 2017-11-21 | 中国石油化工股份有限公司 | Composition epoxy resin and cured obtained epoxide resin material |
| US10786977B2 (en) | 2014-06-04 | 2020-09-29 | Bright Lite Structures Llc | Composite sandwich having a high bending stiffness |
| US10967583B2 (en) | 2015-04-03 | 2021-04-06 | Bright Lite Structures Llc | Apparatus for controllably cutting fibers and related methods |
| CN106589837A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Heat-resisting epoxy resin and carbon fiber composite cured at medium and low temperature and preparation method of composite |
| JPWO2020100785A1 (en) * | 2018-11-12 | 2021-09-27 | 三菱ケミカル株式会社 | Method for manufacturing thermosetting epoxy resin composition, thermosetting molding material, thermosetting molding material, fiber-reinforced composite material |
| JP2021001245A (en) * | 2019-06-20 | 2021-01-07 | 三菱ケミカル株式会社 | Fiber-reinforced epoxy resin composite material and fiber-reinforced plastic |
| CN114179462B (en) * | 2022-02-16 | 2022-06-21 | 北京玻钢院复合材料有限公司 | Self-adhesive composite material honeycomb plate and preparation method thereof |
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