JP2004277481A - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- JP2004277481A JP2004277481A JP2003067850A JP2003067850A JP2004277481A JP 2004277481 A JP2004277481 A JP 2004277481A JP 2003067850 A JP2003067850 A JP 2003067850A JP 2003067850 A JP2003067850 A JP 2003067850A JP 2004277481 A JP2004277481 A JP 2004277481A
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- epoxy resin
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 116
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 59
- 239000003733 fiber-reinforced composite Substances 0.000 claims abstract description 22
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 15
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 239000004697 Polyetherimide Substances 0.000 claims description 14
- 229920001601 polyetherimide Polymers 0.000 claims description 12
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 7
- 229920006393 polyether sulfone Polymers 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 3
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 claims description 3
- VAGOJLCWTUPBKD-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=1)=CC=CC=1N(CC1OC1)CC1CO1 VAGOJLCWTUPBKD-UHFFFAOYSA-N 0.000 claims description 2
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 claims description 2
- 229920006162 poly(etherimide sulfone) Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000012778 molding material Substances 0.000 abstract description 6
- 208000002740 Muscle Rigidity Diseases 0.000 description 11
- 239000000835 fiber Substances 0.000 description 9
- 229920000049 Carbon (fiber) Polymers 0.000 description 8
- 239000004917 carbon fiber Substances 0.000 description 8
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229920001228 polyisocyanate Polymers 0.000 description 5
- 239000005056 polyisocyanate Substances 0.000 description 5
- 239000012783 reinforcing fiber Substances 0.000 description 5
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 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 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 glycidylamino group Chemical group 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229940018563 3-aminophenol Drugs 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000012669 compression test Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 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 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 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
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、エポキシ樹脂組成物、それを用いるプリプレグ及び繊維強化複合成形体に関し、更に詳しくは、繊維強化複合成形材料のマトリックス樹脂として用いた際に剛性及び靭性に優れた繊維強化複合成形体を得ることができるエポキシ樹脂組成物、それを用いるプリプレグ及び繊維強化複合成形体に関する。
【０００２】
【従来の技術】
エポキシ樹脂組成物は、従来より繊維強化複合成形材料用のマトリックス樹脂として使用されている。特に、炭素繊維を強化材繊維とする複合成形材料のマトリックス樹脂としてエポキシ樹脂組成物は広く使用されている。このような複合成形材料から得られる繊維強化複合成形体は、例えばゴルフシャフトや釣竿のようなスポーツ・レジャー用途から、航空機の二次構造材、更には一次構造材に至るまで使用範囲が拡大している。
【０００３】
航空機のような分野に使用されるエポキシ樹脂組成物およびプリプレグとして、樹脂組成物の揮発成分を少なくし、しかも耐熱性を高く、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が提案されている（特許文献１）。
【０００４】
特許文献（１）で提案されている技術は、揮発分の含有率及び硬化時最低粘度が特定範囲のエポキシ樹脂組成物であり、その骨子は（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）熱可塑性樹脂及び（ｅ）芳香族アミン硬化剤を必須成分として含むものである。
【０００５】
しかしながら、従来の繊維強化複合材料成形体は剛性又は靱性のいずれか一方に優れていても、両者を兼ね備えたものはなかった。近年、剛性に加えて更に優れた靭性を兼ね備えた繊維強化複合成形体の要求が高まり、上記など従来技術の改良が望まれている。
【０００６】
【特許文献１】
特開２００１−０３１８３８
【０００７】
【発明が解決しようとする課題】
本発明は、繊維強化複合成形材料のマトリックス樹脂として用いた際に剛性（例えば、圧縮強度）及び靭性（例えば、衝撃後圧縮強度）に優れた繊維強化複合成形体を得ることができるエポキシ樹脂組成物、それを用いたプリプレグ及び繊維強化複合成形体を提供することを課題とする。
【０００８】
【課題を解決するための手段】
上記目的を達成する本発明は、以下に記載のものである。
【０００９】
［１］ 一分子中に少なくとも３個のエポキシ基を有するエポキシ樹脂を８０質量％以上含むエポキシ樹脂（Ａ）１００質量部に対し、熱可塑性樹脂（Ｂ）３０〜５０質量部及び芳香族アミン系硬化剤（Ｃ）２０〜５０質量部を含むことを特徴とするエポキシ樹脂組成物。
【００１０】
［２］ エポキシ樹脂（Ａ）が、テトラグリシジルジアミノジフェニルメタン、Ｎ，Ｎ，Ｏ−トリグリシジル−ｐ−アミノフェノール、Ｎ，Ｎ，Ｏ−トリグリシジル−ｍ−アミノフェノール及びフェノールノボラック型エポキシ樹脂よりなる群から選ばれる少なくとも１種である［１］記載のエポキシ樹脂組成物。
【００１１】
［３］ 熱可塑性樹脂（Ｂ）として、ポリエーテルイミド及びポリエーテルスルホンを含む［１］記載のエポキシ樹脂組成物。
【００１２】
［４］ 芳香族アミン系硬化剤（Ｃ）が、３，３’−ジアミノジフェニルスルホン及び／又は４，４’−ジアミノジフェニルスルホンである［１］記載のエポキシ樹脂組成物。
【００１３】
［５］ ポリエーテルイミドが完全に溶解せず微分散の状態で、且つポリエーテルスルホンが溶解された状態でエポキシ樹脂組成物中に配合されている［２］記載のエポキシ樹脂組成物。
【００１４】
［６］ ［１］記載のエポキシ樹脂組成物を用いたプリプレグ。
【００１５】
［７］ ［６］記載のプリプレグを用いて得られる炭素繊維強化樹脂成形体。
【００１６】
【発明の実施の形態】
本発明のエポキシ樹脂組成物は、一分子中に少なくとも３個のエポキシ基を有するエポキシ樹脂を８０質量％以上含むエポキシ樹脂（Ａ）１００質量部に対し、熱可塑性樹脂（Ｂ）３０〜５０質量部及び芳香族アミン系硬化剤（Ｃ）２０〜５０質量部を含むことを特徴とする。
【００１７】
本発明におけるエポキシ樹脂（Ａ）は、一分子中に少なくとも３個のエポキシ基を有するエポキシ樹脂を８０質量％以上含むものである。
【００１８】
この一分子中に少なくとも３個のエポキシ基を有するエポキシ樹脂としては、例えば、テトラグリシジルジアミノジフェニルメタン（４官能エポキシ樹脂：Ｅｐｉｋｏｔｅ ６０４：ジャパンエポキシレジン株式会社製（登録商標））、フェノールノボラック型エポキシ樹脂（３官能以上のエポキシ樹脂を主成分とする：ＥＰＰＮ−２０１：日本化薬株式会社製（登録商標））、ｍ−アミノフェノール系エポキシ樹脂（３官能エポキシ樹脂ＥＬＭ−１２０：住友化学株式会社製（登録商標））等を挙げることができる。
【００１９】
これらの一分子中に少なくとも３個のエポキシ基を有するエポキシ樹脂（以下、『多官能エポキシ樹脂』ということがある）は、エポキシ樹脂（Ａ）中に８０質量％以上存在することが必要である。この多官能エポキシ樹脂の割合がエポキシ樹脂（Ａ）中８０質量％未満であると、優れた圧縮強度の繊維強化複合成形体を得ることができない。
【００２０】
尚、本発明におけるエポキシ樹脂（Ａ）中には、官能基が１〜２のエポキシ樹脂が２０質量％未満の割合で含まれていてもよい。このようなエポキシ樹脂としては、例えば、ビスフェノールＦ型エポキシ樹脂（２官能エポキシ樹脂：Ｅｐｉｋｏｔｅ ８０７：ジャパンエポキシレジン株式会社製（登録商標））や、ビスフェノールＡ型エポキシ樹脂（２官能エポキシ樹脂：Ｅｐｉｋｏｔｅ ８２８：ジャパンエポキシレジン株式会社製（登録商標））等の２官能エポキシ樹脂を好ましい例として挙げることができる。
【００２１】
本発明における熱可塑性樹脂（Ｂ）は、エンジニアリングプラスチックとして用いられる熱可塑性樹脂であることが好ましく、エポキシ樹脂（Ａ）と相溶するか、或は親和性を有する熱可塑性樹脂が特に好ましい。このような熱可塑性樹脂としては、例えば、ポリアクリレート、ポリイミド、ポリアミド、ポリエーテルイミド（ＰＥＩ）、ポリアミドイミド、ポリアリールエーテル、フェノキシ樹脂、ポリアリールスルホン、ポリエーテルスルホン（ＰＥＳ）、ポリエーテルエーテルケトン（ＰＥＥＫ）、ポリフェニレンエーテル及びポリカーボネートを挙げることができる。これらのうち、ポリエーテルスルホン（ＰＥＳ）とポリエーテルイミド（ＰＥＩ）が好ましく、この２種を併用することが特に好ましい。
【００２２】
本発明において、エポキシ樹脂組成物中に占める熱可塑性樹脂（Ｂ）の割合は、エポキシ樹脂（Ａ）１００質量部に対し３０〜５０質量部であることが必要である。熱可塑性樹脂（Ｂ）の上記割合が５０質量部を超えると、エポキシ樹脂組成物を用いて得られる硬化物の剛性が低下するだけでなく、樹脂組成物の粘度が高くなるため、本発明のエポキシ樹脂組成物を用いて作製したプリプレグの取り扱い性が低下する。また、熱可塑性樹脂（Ｂ）の上記割合が３０質量部未満であると、エポキシ樹脂組成物を用いて得られる硬化物の靭性が低下する。上記の理由から、エポキシ樹脂（Ａ）１００質量部に対する熱可塑性樹脂（Ｂ）の割合は、３５〜４５質量部であることが好ましい。
【００２３】
尚、熱可塑性樹脂（Ｂ）として、ポリエーテルスルホン（ＰＥＳ）とポリエーテルイミド（ＰＥＩ）を併用する場合、ポリエーテルイミドが完全に溶解せず微分散の状態で、且つポリエーテルスルホンが溶解された状態でエポキシ樹脂組成物中に配合されていることが、圧縮強度に代表される剛性の発現と、衝撃後圧縮強度に代表される耐衝撃性を発現を両立させるという理由で好ましい。
【００２４】
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硬化剤（Ｃ）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芳香族アミン化合物である。これらは単独で、或は２種以上の混合物として使用できる。エポキシ樹脂組成物を用いて得られる硬化物の耐熱性をより良好なものとするには、ＤＤＳ或はその誘導体を単独で用いることが好ましい。
【００２５】
本発明において、エポキシ樹脂組成物中に占める芳香族アミン硬化剤（Ｃ）の割合は、エポキシ樹脂（Ａ）１００質量部に対し２０〜５０質量部であることが必要である。芳香族アミン硬化剤（Ｃ）の上記割合が５０質量部を超えると、架橋点数は増加するが架橋密度が低下し、また芳香族アミン硬化剤（Ｃ）の余剰量が多くなるため、このようなエポキシ樹脂組成物を用いて得られる硬化物は剛性及び耐湿熱性が低下する。また、芳香族アミン硬化剤（Ｃ）の上記割合が２０質量部未満であると、架橋点数及び架橋密度ともに低下するため、このようなエポキシ樹脂組成物を用いて得られる硬化物は耐熱性及び耐衝撃性がともに低下する。上記の理由から、エポキシ樹脂（Ａ）１００質量部に対する芳香族アミン硬化剤（Ｃ）の割合は、２５〜４５質量部であることが好ましい。
【００２６】
本発明のエポキシ樹脂組成物は、ポリイソシアネートを成分として含まないことが好ましい。一般に、ポリイソシアネートはエポキシ樹脂に含まれる水酸基と反応することで、増粘或は硬化剤としての効果を示すが、本発明における樹脂組成物の主成分である多官能エポキシ樹脂には水酸基がほとんど含まれないため、ポリイソシアネートを配合することによる効果もほとんどない。従って、本発明のエポキシ樹脂組成物中には、ポリイソシアネートを必要としないが、例えばエポキシ樹脂中の不純物として存在する程度の１０００ｐｐｍ以下の量であれば含まれていてもよい。
【００２７】
本発明のエポキシ樹脂組成物は、上述した（Ａ）、（Ｂ）及び（Ｃ）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、必要に応じて上述の（Ａ）、（Ｂ）及び（Ｃ）以外の公知の硬化剤、熱硬化性樹脂、充填剤、安定剤、難燃剤、顔料等の各種添加剤を含有させてもよい。
【００２８】
本発明のプリプレグは、繊維集合体に本発明のエポキシ樹脂組成物を含浸させることによって得られる。プリプレグ中のエポキシ樹脂組成物の割合は、３０〜５０質量％であることが好ましい。エポキシ樹脂組成物の割合がこの範囲であれば、プリプレグを熱硬化させて得られる繊維強化複合成形体の剛性及び靭性が優れたものになる。
【００２９】
本発明のプリプレグを製造する方法としては、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たいわゆる樹脂フィルムを、繊維集合体の上下に配置し、加熱及び加圧することでエポキシ樹脂組成物を繊維集合体に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を挙げることができる。
【００３０】
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、ガラス繊維等を挙げることができる。これらの強化繊維のうち、炭素繊維が特に好ましい。炭素繊維を用いる場合、ストランドの引張強度は４０００ＭＰａ以上のものが好ましく、４５００ＭＰａ以上のものが特に好ましい。これらの強化繊維は、一方向に引き揃えられた繊維束状、或は織物状の形態で使用することができる。
【００３１】
また、本発明の繊維強化複合成形体は、上記本発明のプリプレグを通常の熱硬化成形、例えば、オートクレーブ成形、または、ホットプレス成形等、により得ることができる。
【００３２】
【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。本実施例及び比較例において各種試験方法は下記に従って行った。
【００３３】
（１）圧縮強度
プリプレグを一方向に６枚積層してバッグ内に入れ、これをオートクレーブ内で１８０℃にて２時間加熱し、硬化させて成形板を作製した。この間オートクレーブ内を圧空で０．５ＭＰａに加圧し、バッグ内を真空（１３ｋＰａ以下）に保った。得られた成形板について、超音波探傷装置にて該成形板の内部にボイド等の欠陥が発生していないことを確認後、ＳＡＣＭＡ ＳＲＭ１Ｒ−９４に準拠して圧縮試験を行い、成形板の圧縮強度［ＭＰａ］を測定した。
【００３４】
尚、本試験では試験片のＶｆ（繊維体積含有率）の影響を大きく受けるため、測定値はＶｆ＝６０％に統一して換算した。
【００３５】
（２）衝撃後圧縮強度
プリプレグを［＋４５°／０°／−４５°／９０°］の方向に４枚積層したものを３セット重ね合わせた１２枚の積層物と、［９０°／−４５°／０°／＋４５°］の方向に４枚積層したもの３セット重ね合わせた１２枚の積層物を、それぞれ９０°方向が合わさるように合計２４枚の積層物としてバッグ内に入れ、これをオートクレーブ内で１８０℃にて２時間加熱し、硬化させて成形板を作製した。この間オートクレーブ内を圧空で０．５ＭＰａに加圧し、バッグ内を真空（１３ｋＰａ以下）に保った。得られた成形板について、超音波探傷装置にて該成形板の内部にボイド等の欠陥が発生していないことを確認後、ＳＡＣＭＡ ＳＲＭ２Ｒ−９４に準拠して圧縮試験を行い、成形板の衝撃後圧縮強度［ＭＰａ］を測定した。
【００３６】
尚、本試験では試験片のＶｆ（繊維体積含有率）の影響が小さいため、測定値はＶｆ換算しない実測値として計算した。
【００３７】
［実施例１〜４］
下記表１に示す組成の（Ａ）成分と（Ｂ）成分の一部（（Ｂ）成分のうちエポキシ樹脂に溶解して配合させる部分）をニーダー中にて加熱・混合させた。次いで、得られた（Ａ）成分の混合物をロールミルに移し、表１に示す（Ｂ）成分の残り（（Ｂ）成分のうちエポキシ樹脂に微粉末として配合させる部分）及び（Ｃ）成分を添加し、良く混練して実施例１〜４のエポキシ樹脂組成物を得た。
【００３８】
次いで、得られたエポキシ樹脂組成物を、炭素繊維束（東邦テナックス株式会社製・ベスファイトＩＭ６００−２４Ｋ（登録商標）・フィラメント数：２４０００本、引張強度：５７９０ＭＰａ、引張弾性率：２８５ＭＰａ）に含浸させて、炭素繊維目付が１９０ｇ／ｍ２、樹脂含有率が３５質量％の一方向プリプレグを得た。これらのプリプレグから成形した成形板の圧縮強度及び衝撃後圧縮強度の測定結果を表１に示す。
【００３９】
【表１】
＊１：実施例１〜４において、ＰＥＩはいずれもエポキシ樹脂組成物に微分散された状態であった。
【００４１】
＊２：繊維体積比率Ｖｆ＝６０％換算値
表１に示した結果から明らかなように、実施例１〜４の本発明のエポキシ樹脂組成物を用いたプリプレグから得られた繊維強化複合成形体は剛性（圧縮強度）及び靭性（衝撃後圧縮強度）のいずれも優れたものであった。
【００４２】
［比較例１〜４］
［Ａ］成分、［Ｂ］成分及び［Ｃ］成分の種類及び量を下記表２に示すものに変えた以外は実施例１と同様にエポキシ樹脂組成物を得た。
【００４３】
次いで、得られたエポキシ樹脂組成物を、実施例１と同様に炭素繊維束に含浸させてプリプレグを得た。これらのプリプレグから成形した成形板の圧縮強度及び衝撃後圧縮強度の測定結果を表２に示す。
【００４４】
【表２】
＊３：比較例４において、ＰＥＩはエポキシ樹脂組成物に微分散された状態であった。
【００４６】
＊４：繊維体積比率Ｖｆ＝６０％換算値
表２に示した結果から明らかなように、比較例１〜４のエポキシ樹脂組成物を用いたプリプレグから得られた繊維強化複合成形体は剛性（圧縮強度）及び靭性（衝撃後圧縮強度）のいずれか、或は両方とも本発明のエポキシ樹脂組成物から得られたものに比べて劣るものであった。
【００４７】
尚、表１及び表２中の各成分は以下に示すものである。
・Ｅｐｉｋｏｔｅ ６０４：テトラグリシジルアミノジフェニルメタン（４官能エポキシ樹脂：ジャパンエポキシレジン株式会社製（登録商標））、
・ＥＰＰＮ−２０１：フェノールノボラック型エポキシ樹脂（３官能以上のエポキシ樹脂を主成分とする：日本化薬株式会社製（登録商標））
・ＥＬＭ−１２０：ｍ−アミノフェノール系エポキシ樹脂（３官能エポキシ樹脂：住友化学株式会社製（登録商標））
・Ｅｐｉｋｏｔｅ ８０７：ビスフェノールＦ型エポキシ樹脂（２官能エポキシ樹脂： ジャパンエポキシレジン株式会社製（登録商標））
・Ｅｐｉｋｏｔｅ ８２８：ビスフェノールＡ型エポキシ樹脂（２官能エポキシ樹脂： ジャパンエポキシレジン株式会社製（登録商標））
・ＰＥＳ：ポリエーテルスルホン（住友化学株式会社製・熱可塑性樹脂）
・ＰＥＩ：ポリエーテルイミド（ジー・イー・プラスチック株式会社製・熱可塑性樹脂）
・３，３’−ＤＤＳ：３，３’−ジアミノジフェニルスルフォン（芳香族アミン系硬化剤）
・４，４’−ＤＤＳ：４，４’−ジアミノジフェニルスルフォン（芳香族アミン系硬化剤）
【００４８】
【発明の効果】
本発明のエポキシ樹脂組成物によれば、繊維強化複合成形材料のマトリックス樹脂として用いた際に剛性及び靭性に優れた繊維強化複合成形体を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an epoxy resin composition, a prepreg and a fiber-reinforced composite molded article using the same, and more particularly, to a fiber-reinforced composite molded article having excellent rigidity and toughness when used as a matrix resin of a fiber-reinforced composite molding material. The present invention relates to an epoxy resin composition that can be obtained, a prepreg using the same, and a fiber-reinforced composite molded article.
[0002]
[Prior art]
Epoxy resin compositions have been conventionally used as matrix resins for fiber-reinforced composite molding materials. In particular, epoxy resin compositions are widely used as matrix resins of composite molding materials using carbon fibers as reinforcing fibers. The range of use of fiber-reinforced composite moldings obtained from such composite molding materials has been expanded from sports and leisure applications such as golf shafts and fishing rods to secondary structural materials for aircraft and even primary structural materials. ing.
[0003]
Epoxy resin compositions and prepregs used in fields such as aircraft, which reduce the volatile components of the resin composition, have high heat resistance, and have good adhesiveness, are used as epoxy for surface materials of self-adhesive honeycomb sandwich panels. A resin composition and a prepreg using the epoxy resin composition have been proposed (Patent Document 1).
[0004]
The technology proposed in Patent Document (1) is an epoxy resin composition in which the content of volatile matter and the minimum viscosity during curing are in a specific range, and the gist thereof is (a) a polyfunctional epoxy resin having a glycidylamino group; (B) An epoxy resin other than (a), (c) a polyisocyanate, (d) a thermoplastic resin, and (e) an aromatic amine curing agent as essential components.
[0005]
However, even though the conventional fiber-reinforced composite material molded article is excellent in either rigidity or toughness, none of them has both. In recent years, there has been an increasing demand for fiber-reinforced composite molded articles having more excellent toughness in addition to rigidity, and improvements in the prior art such as those described above are desired.
[0006]
[Patent Document 1]
JP 2001-031838A
[0007]
[Problems to be solved by the invention]
The present invention provides an epoxy resin composition capable of obtaining a fiber-reinforced composite molded article having excellent rigidity (for example, compressive strength) and toughness (for example, compressive strength after impact) when used as a matrix resin of a fiber-reinforced composite molded material. It is an object to provide a product, a prepreg and a fiber-reinforced composite molded product using the same.
[0008]
[Means for Solving the Problems]
The present invention that achieves the above object is as described below.
[0009]
[1] 30 to 50 parts by mass of a thermoplastic resin (B) and 100 parts by mass of an epoxy resin (A) containing 80% by mass or more of an epoxy resin having at least three epoxy groups in one molecule and an aromatic amine-based resin An epoxy resin composition comprising 20 to 50 parts by mass of a curing agent (C).
[0010]
[2] The epoxy resin (A) comprises tetraglycidyldiaminodiphenylmethane, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-m-aminophenol and phenol novolak type epoxy resin. The epoxy resin composition according to [1], which is at least one member selected from the group.
[0011]
[3] The epoxy resin composition according to [1], wherein the thermoplastic resin (B) contains polyetherimide and polyethersulfone.
[0012]
[4] The epoxy resin composition according to [1], wherein the aromatic amine-based curing agent (C) is 3,3′-diaminodiphenylsulfone and / or 4,4′-diaminodiphenylsulfone.
[0013]
[5] The epoxy resin composition according to [2], wherein the polyetherimide is not completely dissolved but is in a finely dispersed state, and the polyether sulfone is dissolved in the epoxy resin composition.
[0014]
[6] A prepreg using the epoxy resin composition according to [1].
[0015]
[7] A carbon fiber reinforced resin molded product obtained using the prepreg according to [6].
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
The epoxy resin composition of the present invention contains 30 to 50 parts by mass of the thermoplastic resin (B) based on 100 parts by mass of the epoxy resin (A) containing 80% by mass or more of the epoxy resin having at least three epoxy groups in one molecule. And an aromatic amine-based curing agent (C) in an amount of 20 to 50 parts by mass.
[0017]
The epoxy resin (A) in the present invention contains at least 80% by mass of an epoxy resin having at least three epoxy groups in one molecule.
[0018]
Examples of the epoxy resin having at least three epoxy groups in one molecule include tetraglycidyl diaminodiphenylmethane (tetrafunctional epoxy resin: Epikote 604: (registered trademark) manufactured by Japan Epoxy Resin Co., Ltd.), phenol novolak type epoxy resin (Based on a trifunctional or higher epoxy resin: EPPN-201: Nippon Kayaku Co., Ltd. (registered trademark)), m-aminophenol-based epoxy resin (trifunctional epoxy resin ELM-120: manufactured by Sumitomo Chemical Co., Ltd.) (Registered trademark)).
[0019]
The epoxy resin having at least three epoxy groups in one molecule (hereinafter, sometimes referred to as a “polyfunctional epoxy resin”) must be present in the epoxy resin (A) in an amount of 80% by mass or more. . When the proportion of the polyfunctional epoxy resin is less than 80% by mass in the epoxy resin (A), a fiber-reinforced composite molded article having excellent compressive strength cannot be obtained.
[0020]
The epoxy resin (A) in the present invention may contain an epoxy resin having a functional group of 1 to 2 at a ratio of less than 20% by mass. Examples of such an epoxy resin include a bisphenol F type epoxy resin (bifunctional epoxy resin: Epikote 807: manufactured by Japan Epoxy Resin Co., Ltd.) and a bisphenol A type epoxy resin (bifunctional epoxy resin: Epikote 828). : Japan Epoxy Resin Co., Ltd. (registered trademark)) and the like.
[0021]
The thermoplastic resin (B) in the present invention is preferably a thermoplastic resin used as an engineering plastic, and is particularly preferably a thermoplastic resin which is compatible with or has affinity with the epoxy resin (A). Examples of such a thermoplastic resin include polyacrylate, polyimide, polyamide, polyetherimide (PEI), polyamideimide, polyarylether, phenoxy resin, polyarylsulfone, polyethersulfone (PES), and polyetheretherketone. (PEEK), polyphenylene ether and polycarbonate. Of these, polyethersulfone (PES) and polyetherimide (PEI) are preferred, and it is particularly preferred to use these two in combination.
[0022]
In the present invention, the proportion of the thermoplastic resin (B) in the epoxy resin composition needs to be 30 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin (A). When the above proportion of the thermoplastic resin (B) exceeds 50 parts by mass, not only does the rigidity of the cured product obtained using the epoxy resin composition decrease, but also the viscosity of the resin composition increases, so that the present invention The handleability of the prepreg prepared using the epoxy resin composition is reduced. Moreover, when the said ratio of a thermoplastic resin (B) is less than 30 mass parts, the toughness of the hardened | cured material obtained using an epoxy resin composition will fall. For the above reasons, the ratio of the thermoplastic resin (B) to 100 parts by mass of the epoxy resin (A) is preferably from 35 to 45 parts by mass.
[0023]
When polyethersulfone (PES) and polyetherimide (PEI) are used in combination as the thermoplastic resin (B), the polyethersulfone is dissolved in a finely dispersed state without being completely dissolved. It is preferable that the epoxy resin composition is blended in the epoxy resin composition in a state in which both the development of rigidity represented by compressive strength and the impact resistance represented by compressive strength after impact are achieved at the same time.
[0024]
The aromatic amine curing agent (C) used in the epoxy resin composition of the present invention is an aromatic amine compound used as a curing agent for an epoxy resin, such as diaminodiphenylsulfone (DDS) and diaminodiphenylmethane (DDM). These can be used alone or as a mixture of two or more. In order to improve the heat resistance of the cured product obtained using the epoxy resin composition, it is preferable to use DDS or a derivative thereof alone.
[0025]
In the present invention, the proportion of the aromatic amine curing agent (C) in the epoxy resin composition needs to be 20 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin (A). When the proportion of the aromatic amine curing agent (C) exceeds 50 parts by mass, the number of crosslinking points increases, but the crosslinking density decreases, and the excess amount of the aromatic amine curing agent (C) increases. A cured product obtained by using such an epoxy resin composition has reduced rigidity and wet heat resistance. Further, when the proportion of the aromatic amine curing agent (C) is less than 20 parts by mass, both the number of cross-linking points and the cross-linking density decrease, so that the cured product obtained using such an epoxy resin composition has heat resistance and Both impact resistance decreases. For the reasons described above, the ratio of the aromatic amine curing agent (C) to 100 parts by mass of the epoxy resin (A) is preferably 25 to 45 parts by mass.
[0026]
The epoxy resin composition of the present invention preferably does not contain a polyisocyanate as a component. In general, a polyisocyanate shows an effect as a thickener or a curing agent by reacting with a hydroxyl group contained in an epoxy resin, but almost no hydroxyl group is contained in a polyfunctional epoxy resin which is a main component of the resin composition in the present invention. Since it is not contained, there is almost no effect by blending the polyisocyanate. Therefore, the epoxy resin composition of the present invention does not require a polyisocyanate, but may contain, for example, an amount of 1000 ppm or less, which is an amount present as an impurity in the epoxy resin.
[0027]
The epoxy resin composition of the present invention essentially contains the above-mentioned components (A), (B) and (C), but if necessary, the above-mentioned (A) as long as the effects of the present invention are not impaired. ), Known additives other than (B) and (C), various additives such as a thermosetting resin, a filler, a stabilizer, a flame retardant, and a pigment.
[0028]
The prepreg of the present invention is obtained by impregnating a fiber aggregate with the epoxy resin composition of the present invention. The proportion of the epoxy resin composition in the prepreg is preferably 30 to 50% by mass. When the proportion of the epoxy resin composition is within this range, the rigidity and toughness of the fiber-reinforced composite molded product obtained by thermosetting the prepreg will be excellent.
[0029]
As a method for producing the prepreg of the present invention, a so-called resin film obtained by applying the epoxy resin composition of the present invention in the form of a thin film on release paper is disposed above and below the fiber assembly, and heated and pressed. The hot melt method of impregnating the fiber assembly with the epoxy resin composition and the solvent method of impregnating the epoxy resin composition into a varnish using an appropriate solvent and impregnating the varnish into the reinforcing fibers can be exemplified.
[0030]
Examples of the reinforcing fibers that can be used in the prepreg of the present invention include carbon fibers, graphite fibers, aramid fibers, and glass fibers. Among these reinforcing fibers, carbon fibers are particularly preferred. When using carbon fiber, the tensile strength of the strand is preferably 4000 MPa or more, and particularly preferably 4500 MPa or more. These reinforcing fibers can be used in the form of a bundle of fibers aligned in one direction or in the form of a woven fabric.
[0031]
Further, the fiber-reinforced composite molded article of the present invention can be obtained by subjecting the prepreg of the present invention to ordinary thermosetting molding, for example, autoclave molding or hot press molding.
[0032]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. In the examples and comparative examples, various test methods were performed as follows.
[0033]
(1) Six compressive strength prepregs were laminated in one direction and put in a bag, which was heated at 180 ° C. for 2 hours in an autoclave and cured to produce a molded plate. During this time, the inside of the autoclave was pressurized to 0.5 MPa with compressed air, and the inside of the bag was kept at a vacuum (13 kPa or less). With respect to the obtained molded plate, after confirming that no defects such as voids are generated inside the molded plate with an ultrasonic flaw detector, a compression test is performed in accordance with SACMA SRM1R-94, and the compression of the molded plate is performed. The strength [MPa] was measured.
[0034]
In addition, in this test, since the influence of Vf (fiber volume content) of the test piece was greatly affected, the measured value was uniformly converted to Vf = 60%.
[0035]
(2) Twelve laminates obtained by laminating four sets of four layers of the post-impact compressive strength prepreg in the [+ 45 ° / 0 ° / −45 ° / 90 °] direction, and [90 ° / −45]. [0 ° / 0 ° / + 45 °], 12 sets of 3 sets of four sets stacked in the direction of 90 ° are put in a bag as a total of 24 sheets so that the 90 ° directions are aligned. It was heated at 180 ° C. for 2 hours in an autoclave and cured to produce a molded plate. During this time, the inside of the autoclave was pressurized to 0.5 MPa with compressed air, and the inside of the bag was kept at a vacuum (13 kPa or less). For the obtained molded plate, after confirming that no defects such as voids have occurred inside the molded plate with an ultrasonic flaw detector, a compression test is performed in accordance with SACMA SRM2R-94, and the impact of the molded plate is measured. After compression strength [MPa] was measured.
[0036]
In this test, since the influence of Vf (fiber volume content) of the test piece was small, the measured value was calculated as an actually measured value without Vf conversion.
[0037]
[Examples 1 to 4]
The components (A) and (B) of the compositions shown in Table 1 below (parts of the component (B) to be dissolved and mixed in the epoxy resin) were heated and mixed in a kneader. Next, the obtained mixture of the component (A) was transferred to a roll mill, and the remaining component (B) of the component (B) shown in Table 1 (part of the component (B) to be blended into the epoxy resin as a fine powder) and the component (C) were added. And kneaded well to obtain the epoxy resin compositions of Examples 1 to 4.
[0038]
Next, the obtained epoxy resin composition is impregnated into a carbon fiber bundle (Vesfight IM600-24K (registered trademark) manufactured by Toho Tenax Co., Ltd., number of filaments: 24,000, tensile strength: 5790 MPa, tensile elastic modulus: 285 MPa). Thus, a unidirectional prepreg having a carbon fiber weight of 190 g / m 2 and a resin content of 35% by mass was obtained. Table 1 shows the measurement results of the compressive strength and the compressive strength after impact of the molded plate molded from these prepregs.
[0039]
[Table 1]
* 1: In Examples 1 to 4, PEI was in a state of being finely dispersed in the epoxy resin composition.
[0041]
* 2: Fiber volume ratio Vf = 60% conversion value As is clear from the results shown in Table 1, a fiber-reinforced composite molded article obtained from the prepreg using the epoxy resin composition of the present invention of Examples 1 to 4. Was excellent in both rigidity (compression strength) and toughness (compression strength after impact).
[0042]
[Comparative Examples 1-4]
An epoxy resin composition was obtained in the same manner as in Example 1, except that the types and amounts of the components [A], [B] and [C] were changed to those shown in Table 2 below.
[0043]
Next, the obtained epoxy resin composition was impregnated into a carbon fiber bundle in the same manner as in Example 1 to obtain a prepreg. Table 2 shows the measurement results of the compressive strength and the compressive strength after impact of a molded plate formed from these prepregs.
[0044]
[Table 2]
* 3: In Comparative Example 4, PEI was finely dispersed in the epoxy resin composition.
[0046]
* 4: Fiber volume ratio Vf = 60% conversion value As is clear from the results shown in Table 2, the fiber-reinforced composite molded body obtained from the prepreg using the epoxy resin compositions of Comparative Examples 1 to 4 has rigidity ( Either or both of the compression strength) and the toughness (compression strength after impact) were inferior to those obtained from the epoxy resin composition of the present invention.
[0047]
In addition, each component in Table 1 and Table 2 is shown below.
-Epikote 604: tetraglycidylaminodiphenylmethane (tetrafunctional epoxy resin: (registered trademark) manufactured by Japan Epoxy Resin Co., Ltd.),
EPPN-201: phenol novolak type epoxy resin (based on trifunctional or higher epoxy resin: Nippon Kayaku Co., Ltd. (registered trademark))
ELM-120: m-aminophenol-based epoxy resin (trifunctional epoxy resin: (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.)
-Epikote 807: bisphenol F type epoxy resin (bifunctional epoxy resin: Japan Epoxy Resin Co., Ltd. (registered trademark))
-Epikote 828: bisphenol A type epoxy resin (bifunctional epoxy resin: Japan Epoxy Resin Co., Ltd. (registered trademark))
-PES: polyether sulfone (thermoplastic resin manufactured by Sumitomo Chemical Co., Ltd.)
-PEI: Polyetherimide (thermoplastic resin manufactured by GE Plastics Co., Ltd.)
-3,3'-DDS: 3,3'-diaminodiphenyl sulfone (aromatic amine-based curing agent)
· 4,4'-DDS: 4,4'-diaminodiphenylsulfone (aromatic amine-based curing agent)
[0048]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to the epoxy resin composition of this invention, when used as a matrix resin of a fiber reinforced composite molding material, a fiber reinforced composite molded article excellent in rigidity and toughness can be obtained.
Claims (7)
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| JP2003067850A JP4475880B2 (en) | 2003-03-13 | 2003-03-13 | Epoxy resin composition |
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| WO2006095516A1 (en) * | 2005-03-09 | 2006-09-14 | The Yokohama Rubber Co., Ltd. | Curable resin composition, prepreg and composite material using same |
| JP2006291095A (en) * | 2005-04-13 | 2006-10-26 | Yokohama Rubber Co Ltd:The | Epoxy resin composition for fiber reinforced composite materials |
| WO2007034679A1 (en) * | 2005-09-22 | 2007-03-29 | Toho Tenax Co., Ltd. | Resin composition for radiation curing and prepreg |
| WO2007125926A1 (en) * | 2006-04-25 | 2007-11-08 | The Yokohama Rubber Co., Ltd. | Epoxy resin composition for fiber-reinforced composite material |
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| JP2010505990A (en) * | 2006-10-02 | 2010-02-25 | ヘクセル コンポジット、リミテッド | Composite materials with improved performance |
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