JPS6354738B2 - - Google Patents
Info
- Publication number
- JPS6354738B2 JPS6354738B2 JP15326781A JP15326781A JPS6354738B2 JP S6354738 B2 JPS6354738 B2 JP S6354738B2 JP 15326781 A JP15326781 A JP 15326781A JP 15326781 A JP15326781 A JP 15326781A JP S6354738 B2 JPS6354738 B2 JP S6354738B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- weight
- manufactured
- prepreg
- 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.)
- Expired
Links
- 239000003822 epoxy resin Substances 0.000 claims description 44
- 229920000647 polyepoxide Polymers 0.000 claims description 44
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000004952 Polyamide Substances 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 239000004760 aramid Substances 0.000 claims description 7
- 229920003235 aromatic polyamide Polymers 0.000 claims description 7
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- -1 urea compound Chemical class 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 241000264877 Hippospongia communis Species 0.000 description 21
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 229920003319 Araldite® Polymers 0.000 description 2
- 102100039389 Hepatoma-derived growth factor-related protein 3 Human genes 0.000 description 2
- 101710161031 Hepatoma-derived growth factor-related protein 3 Proteins 0.000 description 2
- 229920013646 Hycar Polymers 0.000 description 2
- 229920000271 Kevlar® Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229920003369 Kevlar® 49 Polymers 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229920001494 Technora Polymers 0.000 description 1
- UUQQGGWZVKUCBD-UHFFFAOYSA-N [4-(hydroxymethyl)-2-phenyl-1h-imidazol-5-yl]methanol Chemical compound N1C(CO)=C(CO)N=C1C1=CC=CC=C1 UUQQGGWZVKUCBD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004950 technora Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Reinforced Plastic Materials (AREA)
Description
本発明は、特にハニカムとの接着性と低温硬化
性に優れたエポキシ樹脂組成物を含浸してなる芳
香族ポリアミド繊維プリプレグに関する。
近時、ハニカムサンドイツチパネルは軽量で、
かつ強度、剛性が高く航空機の内装材等に多く用
いられてきている。このハニカムサンドイツチパ
ネルは、航空機の軽量化の要求からフイルム状接
着剤を用いないで、ハニカムとプリプレグとの直
接接着により作ることが指向されるようになつて
きた。フイルム状接着剤を用いない場合には、プ
リプレグの硬化と同時に流れ出た樹脂がハニカム
とプリプレグとの接着剤として働くため、プリプ
レグのマトリツクス樹脂は接着性に優れているこ
とが必要であり、かつ表面材としてのコンポジツ
ト性能、特に層間剪断強度、圧縮強度等が高いも
のでなければならない。
このような表面材として芳香族ポリアミド繊維
強化プラスチツクス（以下KFRPという。）を用
いたハニカムサンドイツチパネルは軽量で高強
度、高剛性であり優れたものであることが予測さ
れるが、ここに使用されるマトリツクス樹脂とし
てのエポキシ樹脂には、高いコンポジツト性能及
びハニカムとの接着力が要求される。
本発明者らは、かかる要求を満足するエポキシ
樹脂組成物を開発したが、このものを芳香族ポリ
アミド繊維に含浸させると、優れたコンポジツト
性能を与えるプリプレグが得られることを見出し
た。
本発明は下記のとおりである。
下記(a)〜(d)の成分
(a) 少くとも60重量％のビスフエノールＡ型エポ
キシ樹脂を含むエポキシ樹脂
(b) 両末端にカルボキシル基を有する液状のブタ
ジエン―アクリロニトリル共重合体とエポキシ
樹脂との反応生成物
(c) ジシアンジアミド
(d) 末端にアミノ基を有する液状又は半固形状ポ
リアミド
を含むエポキシ樹脂組成物を含浸してなる芳香族
ポリアミド繊維プリプレグ。
本発明のプリプレグを用いて製造したハニカム
サンドイツチパネルは表面材とハニカムとの直接
接着性に優れ、またKFRPのコンポジツト性能も
優れている。また、本発明におけるエポキシ樹脂
組成物は、低温での硬化速度が大きく、ゲルタイ
ムは例えば100℃、約10〜15分であり、従来の通
常の場合に比し半分以下である。
本発明における(a)成分のエポキシ樹脂はビスフ
エノールＡ型エポキシ樹脂を少くとも60重量％含
んでいなければならない。残部は他のエポキシ樹
脂例えばノボラツク型エポキシ樹脂、グリシジル
アミン型エポキシ樹脂等の１種又は２種以上であ
る。ビスフエノールＡ型エポキシ樹脂の比率が60
重量％未満のときは芳香族ポリアミド繊維プリプ
レグとハニカムとの接着力が低下する。
ビスフエノールＡ型エポキシ樹脂としては例え
ばエピコート828（シエル化学社製）、エピコート
834（同）、DER332（ダウケミカル社製）等があ
る。また難燃性を付与するための臭素化ビスフエ
ノールＡ型エポキシ樹脂例えばDER511（ダウケ
ミカル社製）、アラルダイト8011（チバ・ガイギー
社製）等を用いることもできる。
同(b)成分は、両末端にカルボキシル基を有する
液状のブタジエン―アクリロニトリル共重合体、
例えばハイカ―CTBN1300×８、CTBN1300×
15、CTBN1300×13、CTBN1300×９等（B.F.
グツドリツチケミカル社製）とエポキシ樹脂との
反応生成物である。反応はトリフエニルホスフイ
ンを触媒として170℃で１〜２時間行われる。こ
の反応に供するエポキシ樹脂は種類に制限がな
く、例えばビスフエノールＡ型エポキシ樹脂が好
適に使用される。
同(d)成分の末端にアミノ基を有する液状又は半
固形状ポリアミドは、不飽和脂肪酸を２量体化さ
せた、いわゆるダイマー酸と、ポリアミンとを反
応させて得られる反応性を有する熱可塑性樹脂で
ある。このポリアミドの液状のものは粘度約300
〜70000cpsである。このポリアミドは、例えばト
ーマイド（富士化成工業社製）又はバーサミド
（第一ゼネラル社製）の商標で販売されている。
固形のポリアミドはエポキシ樹脂と相溶性が悪く
不適当である。また末端にアミノ基のないポリア
ミドは、エポキシ樹脂との反応性がなく硬化物の
物性を著しく低下させ、低温硬化性の効果も小さ
く好ましくない。
本発明におけるエポキシ樹脂組成物の混合比は
次の範囲がよい。すなわち、(a)成分のエポキシ樹
脂100重量部に対し(b)成分の反応生成物３〜20、
好ましくは５〜15重量部、(c)成分のジシアンジア
ミド１〜10、好ましくは２〜６重量部、(d)成分の
ポリアミド１〜10、好ましくは２〜６重量部であ
る。
本発明においては硬化剤ジシアンジアミドとと
もに硬化促進剤として尿素化合物例えば３―
（３，４―ジクロロフエニル）−１，１―ジメチル
尿素、クロロフエニル、−１，１―ジメチル尿素、
又は、イミダゾール化合物例えば２―フエニル−
４―メチル−５―ビトロキシメチルイミダゾー
ル、２―フエニル−４，５―ジヒドロキシメチル
イミダゾール等を添加することができる。
その他、必要に応じ例えば難燃剤（酸化アンチ
モンなど）等を加えてもよい。
このような樹脂組成物を含浸してなる本発明の
プリプレグは、前記ハニカムサンドイツチパネル
用途以外の成形物を製造するものにも使用可能で
ある。また、本発明の芳香族ポリアミド繊維プリ
プレグは、マトリツクス樹脂として同じエポキシ
樹脂組成物を含浸させた炭素繊維プリプレグと組
合せ使用して優れたハイブリツト材を提供するこ
とができる。
次に、本発明を実施例によつて説明する。
実施例 １
ブタジエン―アクリロニトリル共重合体として
ハイカ―CTBN1300×13（B.F.グツドリツチ ケ
ミカル社製）100ｇとエポキシ樹脂（ビスフエノ
ールＡ型）としてエピコート828（シエル化学社
製）30ｇの混合物に触媒としてトリフエニルホス
フイン0.5ｇを添加して170℃で１時間30分反応さ
せて反応生成物(b)成分130ｇを得た。
この反応生成物に、(a)成分エポキシ樹脂として
エピコート828（シエル化学社製）500ｇ、エピコ
ート834（同）150ｇ、臭素化ビスフエノールＡ型
エポキシ樹脂DER511（ダウケミカル社製）250
ｇ、フエノールノボラツク型エポキシEPN1138
（チバ・ガイギー社製）100ｇ、(c)成分硬化剤とし
てジシアンジアミド40ｇ、硬化促進剤として３―
（３，４―ジクロロフエニル）−１，１―ジメチル
尿素50ｇ、(d)成分ポリアミドとしてトーマイド
215×（富士化成工業社製）40ｇ、及び難燃剤とし
て酸化アンチモン30ｇを加えて、エポキシ樹脂組
成物を得た。このエポキシ樹脂組成物の成分重量
比は(a)／(b)／(c)／(d)＝100／13／４／４である。
このものをアセトンとメチルセロソルブの混合
溶剤に溶解し、50重量％溶液とした。
この樹脂溶液をケブラー49（デユポン社製）に
含浸させた後80℃で１時間乾燥させて樹脂含有量
42重量％のプリプレグを得た。
このプリプレグをガラス繊維強化プラスチツク
スハニカムHRP―３／16―4.0（ヘキセル社製）
の両面に各２枚積層し、130℃で90分、３Kg／cm2
の条件でオートクレーブ成形しハニカムサンドイ
ツチパネルを作つた。またこのプリプレグを積層
し同一条件で成形して成形板を作つた。
ハニカムサンドイツチパネルについて接着力を
試験するため平面引張強度を測定し（Flatwise
Tension、MIL Specification 401Bの試験方法
による）、また成形板についてコンポジツト性能
を試験するため層間剪断強度（ILSS）を測定し
た。測定結果は下記第１表に示すとおりであつ
た。
実施例 ２
前記実施例１と同様にしてハイカ―CTBNと
エポキシ樹脂との反応生成物(b)成分を作り、これ
に(a)成分としてエピコート828の400ｇ、DER511
の250ｇ、EPN1138の350ｇを加えた以外は実施
例１と同じ硬化剤、硬化促進剤を配合し樹脂組成
物を得た。これものを実施例１と同様にしてケブ
ラーに含浸させてプリプレグを作つた。さらに成
形板とハニカムサンドイツチパネルを作つた。こ
れらの特性は下記第１表に示すとおりであつた。
実施例 ３
ブタジエン―アクリロニトリル共重合体として
ハイカ―CTBN1300×13（B.F.グツドリツチ ケ
ミカル社製）100ｇとエポキシ樹脂（ビスフエノ
ールＡ型）としてエピコート828（シエル化学社
製）30ｇの混合物に触媒としてトリフエニルホス
フイン0.5ｇを添加し170℃で１時間30分反応させ
て反応生成物(b)成分130ｇを得た。
この反応生成物に、(a)成分エポキシ樹脂として
エピコート828（シエル化学社製）500ｇ、エピコ
ート834（同）150ｇ、臭素化ビスフエノールＡ型
エポキシDER511（ダウケミカル社製）250ｇ、フ
エノールノボラツク型エポキシEPN1138（チバ・
ガイギー社製）100ｇ、(c)成分硬化剤としてジシ
アンジアミド40ｇ、硬化促進剤として３―（３，
４―ジクロロフエニル）−１，１―ジメチル尿素
50ｇ、(d)成分ポリアミドとしてトーマイド215×
（富士化成工業社製）40ｇ、及び難燃剤として酸
化アンチモン30ｇを加えて、エポキシ樹脂組成物
を得た。このエポキシ樹脂組成物の成分重量比は
(a)／(b)／(c)／(d)＝100／13／４／４である。この
ものをアセトンとメチルセロソルブの混合溶剤に
溶解し、50重量％溶液とした。この樹脂溶液をテ
クノーラ（帝人社製）に含浸させた後80℃で１時
間乾燥させて樹脂含有量42重量％のプリプレグを
得た。このプリプレグをガラス繊維強化プラスチ
ツクスハニカムHRP―３／16―4.0（ヘキセル社
製）の両面に各２枚積層し130℃で90、３Kg／cm2
の条件でオートクレーブ成形しハニカムサンドイ
ツチパネルを作つた。またこのプリプリグを積層
し同一条件で成形して成形板を作つた。ハニカム
サンドイツチパネルについて接着力を試験するた
め平面引張強度を測定し（Flatwise Tension、
MIL Specification401Bの試験方法による）、ま
た成形板についてコンポジツト性能を試験するた
め層間剪断強度（ILSS）を測定した。測定結果
は下記第１表に示すとおりであつた。
比較例 １
〔(a)成分のエポキシ樹脂中のビスフエノールＡ
型エポキシ樹脂の含量が50重量％〕
前記実施例１と同様にしてハイカ―CTBNと
エポキシ樹脂の反応生成物を作り、これに(a)成分
としてＮ，Ｎ，N′，N′―テトラグリシジルジア
ミノジフエニルメタン（アラルダイトMY 720チ
バ・ガイギー社製）500ｇ、エピコート828の250
ｇ、DER 511の250ｇを加えた以外は実施例１と
同じ硬化剤及び硬化促進剤を配合し、得られた樹
脂組成物を実施例１と同様にしてケブラーに含浸
させてプリプレグを作つた。さらにこのプリプレ
グから成形板とハニカムサンドイツチパネルを作
つた。これらの物性は第１表の通りであつた。
The present invention particularly relates to an aromatic polyamide fiber prepreg impregnated with an epoxy resin composition that has excellent adhesiveness to honeycombs and low-temperature curability. Nowadays, honeycomb sanderch panels are lightweight,
It also has high strength and rigidity, and has been widely used as interior materials for aircraft. Due to the demand for reducing the weight of aircraft, it has become increasingly desirable to manufacture honeycomb sand german panels by directly adhering honeycomb and prepreg without using a film adhesive. If a film adhesive is not used, the resin flowing out at the same time as the prepreg hardens will act as an adhesive between the honeycomb and the prepreg, so the prepreg matrix resin must have excellent adhesive properties, and the surface The composite must have high performance as a material, especially interlaminar shear strength and compressive strength. It is expected that honeycomb sandwich panels using aromatic polyamide fiber-reinforced plastics (hereinafter referred to as KFRP) as a surface material will be lightweight, have high strength, and high rigidity, and will be excellent. The epoxy resin used as the matrix resin is required to have high composite performance and adhesive strength with the honeycomb. The present inventors have developed an epoxy resin composition that satisfies these requirements, and have discovered that when aromatic polyamide fibers are impregnated with this composition, a prepreg that provides excellent composite performance can be obtained. The present invention is as follows. Components (a) to (d) below (a) Epoxy resin containing at least 60% by weight of bisphenol A type epoxy resin (b) Liquid butadiene-acrylonitrile copolymer having carboxyl groups at both ends and epoxy resin (c) dicyandiamide (d) An aromatic polyamide fiber prepreg impregnated with an epoxy resin composition containing a liquid or semi-solid polyamide having an amino group at its terminal. The honeycomb sandwich panel manufactured using the prepreg of the present invention has excellent direct adhesion between the surface material and the honeycomb, and also has excellent KFRP composite performance. Furthermore, the epoxy resin composition of the present invention has a high curing speed at low temperatures, and the gel time is, for example, about 10 to 15 minutes at 100°C, which is less than half that of the conventional case. The epoxy resin component (a) in the present invention must contain at least 60% by weight of bisphenol A type epoxy resin. The remainder is one or more other epoxy resins such as novolac type epoxy resins and glycidylamine type epoxy resins. The ratio of bisphenol A type epoxy resin is 60
When the amount is less than % by weight, the adhesive strength between the aromatic polyamide fiber prepreg and the honeycomb decreases. Examples of bisphenol A-type epoxy resins include Epicote 828 (manufactured by Ciel Chemical Co., Ltd.), Epicote
834 (same), DER332 (manufactured by Dow Chemical Company), etc. Furthermore, brominated bisphenol A type epoxy resins such as DER511 (manufactured by Dow Chemical Company) and Araldite 8011 (manufactured by Ciba-Geigy Company) can also be used to impart flame retardance. Component (b) is a liquid butadiene-acrylonitrile copolymer having carboxyl groups at both ends;
For example, hiker-CTBN1300×8, CTBN1300×
15, CTBN1300×13, CTBN1300×9 etc. (BF
(manufactured by Gutsudoritsuchi Chemical Co., Ltd.) and epoxy resin. The reaction is carried out at 170° C. for 1 to 2 hours using triphenylphosphine as a catalyst. There are no restrictions on the type of epoxy resin used in this reaction, and for example, bisphenol A type epoxy resin is preferably used. The liquid or semi-solid polyamide having an amino group at the end of component (d) is a reactive thermoplastic obtained by reacting a so-called dimer acid, which is a dimerization of unsaturated fatty acids, with a polyamine. It is resin. This liquid polyamide has a viscosity of approximately 300
~70000cps. This polyamide is sold, for example, under the trademark Tomide (manufactured by Fuji Kasei Kogyo Co., Ltd.) or Versamide (manufactured by Daiichi General Co., Ltd.).
Solid polyamide has poor compatibility with epoxy resins and is therefore unsuitable. Further, polyamides without amino groups at the terminals have no reactivity with epoxy resins, significantly reduce the physical properties of the cured product, and have a small low-temperature curability effect, which is not preferred. The mixing ratio of the epoxy resin composition in the present invention is preferably in the following range. That is, 3 to 20 parts of the reaction product of component (b) to 100 parts by weight of the epoxy resin of component (a),
The amount is preferably 5 to 15 parts by weight, the component (c) dicyandiamide 1 to 10, preferably 2 to 6 parts by weight, and the component (d) polyamide 1 to 10, preferably 2 to 6 parts by weight. In the present invention, a urea compound such as 3-
(3,4-dichlorophenyl)-1,1-dimethylurea, chlorophenyl, -1,1-dimethylurea,
or imidazole compounds such as 2-phenyl-
4-methyl-5-bitroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. can be added. In addition, for example, a flame retardant (antimony oxide, etc.) may be added as necessary. The prepreg of the present invention impregnated with such a resin composition can also be used for manufacturing molded articles other than the honeycomb sanderch panel. Further, the aromatic polyamide fiber prepreg of the present invention can be used in combination with a carbon fiber prepreg impregnated with the same epoxy resin composition as a matrix resin to provide an excellent hybrid material. Next, the present invention will be explained with reference to examples. Example 1 A mixture of 100 g of Hycar CTBN1300×13 (manufactured by BF Gutdrich Chemical Co., Ltd.) as a butadiene-acrylonitrile copolymer and 30 g of Epicote 828 (manufactured by Schiel Chemical Co., Ltd.) as an epoxy resin (bisphenol A type) was added with triphenylphosph as a catalyst. After adding 0.5 g of inine, the mixture was reacted at 170° C. for 1 hour and 30 minutes to obtain 130 g of reaction product component (b). To this reaction product, 500 g of Epicoat 828 (manufactured by Ciel Chemical Co., Ltd.), 150 g of Epicoat 834 (manufactured by Ciel Chemical Co., Ltd.) as the (a) component epoxy resin, and 250 g of brominated bisphenol A type epoxy resin DER511 (manufactured by Dow Chemical Co., Ltd.)
g. Phenol novolac type epoxy EPN1138
(manufactured by Ciba Geigy) 100g, (c) component dicyandiamide 40g as curing agent, 3- as curing accelerator
(3,4-dichlorophenyl)-1,1-dimethylurea 50g, Tomide as component (d) polyamide
40 g of 215x (manufactured by Fuji Kasei Kogyo Co., Ltd.) and 30 g of antimony oxide as a flame retardant were added to obtain an epoxy resin composition. The component weight ratio of this epoxy resin composition is (a)/(b)/(c)/(d)=100/13/4/4. This product was dissolved in a mixed solvent of acetone and methyl cellosolve to form a 50% by weight solution. This resin solution was impregnated into Kevlar 49 (manufactured by DuPont) and dried at 80℃ for 1 hour to reduce the resin content.
A 42% by weight prepreg was obtained. This prepreg is made of glass fiber reinforced plastic honeycomb HRP-3/16-4.0 (manufactured by Hexel).
Laminated two sheets each on both sides, heated at 130℃ for 90 minutes, 3Kg/cm 2
A honeycomb sandwich panel was made by autoclave molding under the following conditions. In addition, this prepreg was laminated and molded under the same conditions to make a molded plate. Flatwise tensile strength was measured to test the adhesion of honeycomb sandwich panels (Flatwise
tension (according to the test method of MIL Specification 401B) and interlaminar shear strength (ILSS) was measured on the formed plates to test composite performance. The measurement results were as shown in Table 1 below. Example 2 A reaction product (b) of Hiker CTBN and an epoxy resin was prepared in the same manner as in Example 1, and 400 g of Epicote 828 and DER511 were added to this as the (a) component.
A resin composition was obtained by blending the same curing agent and curing accelerator as in Example 1, except that 250 g of EPN1138 and 350 g of EPN1138 were added. This material was impregnated with Kevlar to prepare a prepreg in the same manner as in Example 1. In addition, we made molded boards and honeycomb sandwich panels. These properties were as shown in Table 1 below. Example 3 A mixture of 100 g of Hycar CTBN 1300 x 13 (manufactured by BF Gutdrich Chemical Co., Ltd.) as a butadiene-acrylonitrile copolymer and 30 g of Epicote 828 (manufactured by Schiel Chemical Co., Ltd.) as an epoxy resin (bisphenol A type) was added with triphenylphosph as a catalyst. 0.5 g of inine was added and the mixture was reacted at 170° C. for 1 hour and 30 minutes to obtain 130 g of reaction product component (b). To this reaction product, as the (a) component epoxy resin, 500 g of Epicote 828 (manufactured by Schiel Chemical Co., Ltd.), 150 g of Epicote 834 (same), 250 g of brominated bisphenol A type epoxy DER511 (manufactured by Dow Chemical Company), and phenol novolak type Epoxy EPN1138 (Ciba)
100g (manufactured by Geigy), 40g of dicyandiamide as a curing agent (c), and 3-(3,
4-dichlorophenyl)-1,1-dimethylurea
50g, Tomide 215x as (d) component polyamide
(manufactured by Fuji Kasei Kogyo Co., Ltd.) and 30 g of antimony oxide as a flame retardant were added to obtain an epoxy resin composition. The component weight ratio of this epoxy resin composition is
(a)/(b)/(c)/(d)=100/13/4/4. This product was dissolved in a mixed solvent of acetone and methyl cellosolve to form a 50% by weight solution. Technora (manufactured by Teijin) was impregnated with this resin solution and dried at 80° C. for 1 hour to obtain a prepreg with a resin content of 42% by weight. Two sheets of this prepreg were laminated on each side of a glass fiber reinforced plastic honeycomb HRP-3/16-4.0 (manufactured by Hexel) and heated to 90.3 kg/cm 2 at 130°C.
A honeycomb sandwich panel was made by autoclave molding under the following conditions. In addition, this prepreg was laminated and molded under the same conditions to make a molded plate. Flatwise tensile strength was measured to test the adhesion of honeycomb sandwich panels (Flatwise Tension,
(according to the test method of MIL Specification 401B), and the interlaminar shear strength (ILSS) was also measured on the formed plates to test the composite performance. The measurement results were as shown in Table 1 below. Comparative Example 1 [Bisphenol A in the epoxy resin of component (a)]
The content of type epoxy resin is 50% by weight] A reaction product of Hiker-CTBN and epoxy resin was prepared in the same manner as in Example 1, and N,N,N',N'-tetraglycidyl was added as component (a). Diaminodiphenylmethane (Araldite MY 720 manufactured by Ciba Geigy) 500g, Epicote 828 250
The same curing agent and curing accelerator as in Example 1 were mixed, except that 250 g of DER 511 was added, and the resulting resin composition was impregnated into Kevlar to prepare a prepreg in the same manner as in Example 1. Furthermore, molded plates and honeycomb sand germanchi panels were made from this prepreg. These physical properties were as shown in Table 1.
【表】
第１表の結果から明らかなように、実施例の場
合、ILSSはは比較例と殆んど差がないが、ハニ
カムサンドイツチパネルの平面引張強度が比較例
に比し顕著に向上しており、したがつて、本発明
のプリプレグは特にハニカムサンドイツチパネル
の製造に有効に使用することができる。[Table] As is clear from the results in Table 1, in the case of the example, there is almost no difference in ILSS from the comparative example, but the plane tensile strength of the honeycomb sanderch panel is significantly improved compared to the comparative example. Therefore, the prepreg of the present invention can be particularly effectively used in the production of honeycomb sandwich panels.
Claims (1)
キシ樹脂を含むエポキシ樹脂 (b) 両末端にカルボキシル基を有する液状のブタ
ジエン―アクリロニトリル共重合体とエポキシ
樹脂との反応生成物 (c) ジシアンジアミド (d) 末端にアミノ基を有する液状又は半固形状ポ
リアミド を含むエポキシ樹脂組成物を含浸してなる芳香族
ポリアミド繊維プリプレグ。 ２ エポキシ樹脂組成物が前記(a)のエポキシ樹脂
100重量部、(b)の反応生成物３〜20重量部、(c)の
ジシアンジアミド１〜10重量部及び(d)のポリアミ
ド１〜10重量部を含むものである特許請求の範囲
１のプリプレグ。 ３ エポキシ樹脂組成物が尿素化合物又はイミダ
ゾール化合物を含むものである特許請求の範囲１
のプリプレグ。[Scope of Claims] 1 Components (a) to (d) below (a) An epoxy resin containing at least 60% by weight of bisphenol A type epoxy resin (b) Liquid butadiene having carboxyl groups at both ends. An aromatic polyamide fiber prepreg impregnated with an epoxy resin composition containing a reaction product of an acrylonitrile copolymer and an epoxy resin (c) dicyandiamide (d) a liquid or semisolid polyamide having an amino group at the terminal. 2 The epoxy resin composition is the epoxy resin of (a) above.
100 parts by weight of the reaction product (b), 3 to 20 parts by weight of the reaction product (b), 1 to 10 parts by weight of dicyandiamide (c), and 1 to 10 parts by weight of the polyamide (d). 3 Claim 1 in which the epoxy resin composition contains a urea compound or an imidazole compound
prepreg.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15326781A JPS5853925A (en) | 1981-09-28 | 1981-09-28 | Aromatic polyamide fiber prepreg |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15326781A JPS5853925A (en) | 1981-09-28 | 1981-09-28 | Aromatic polyamide fiber prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5853925A JPS5853925A (en) | 1983-03-30 |
| JPS6354738B2 true JPS6354738B2 (en) | 1988-10-31 |
Family
ID=15558715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15326781A Granted JPS5853925A (en) | 1981-09-28 | 1981-09-28 | Aromatic polyamide fiber prepreg |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5853925A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4578424A (en) * | 1985-05-03 | 1986-03-25 | Ashland Oil, Inc. | High performance two-component epoxy structural adhesives with chemical thixotropy |
| FR2589472B1 (en) * | 1985-10-31 | 1988-02-26 | Charbonnages Ste Chimique | PROCESS FOR PRODUCING COMPOSITIONS BASED ON EPOXY RESINS |
| JP6202978B2 (en) * | 2013-10-17 | 2017-09-27 | 日産自動車株式会社 | Fiber-reinforced composite material and pressure vessel using the same |
-
1981
- 1981-09-28 JP JP15326781A patent/JPS5853925A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5853925A (en) | 1983-03-30 |
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