JPH0496921A - Resin composition for composite material, intermediate material and composite material - Google Patents
Resin composition for composite material, intermediate material and composite materialInfo
- Publication number
- JPH0496921A JPH0496921A JP21440190A JP21440190A JPH0496921A JP H0496921 A JPH0496921 A JP H0496921A JP 21440190 A JP21440190 A JP 21440190A JP 21440190 A JP21440190 A JP 21440190A JP H0496921 A JPH0496921 A JP H0496921A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- composite material
- resin composition
- epoxy resin
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims description 31
- 239000011342 resin composition Substances 0.000 title claims description 17
- 239000000463 material Substances 0.000 title claims description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000012783 reinforcing fiber Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 3
- 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 abstract description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 229920003319 Araldite® Polymers 0.000 description 7
- 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 6
- 238000000034 method Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 238000001723 curing Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は複合材料用樹脂組成物およびそれを補強繊維に
含浸して得られる中間材並びに中間材を成形して得られ
る複合材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a resin composition for composite materials, an intermediate material obtained by impregnating reinforcing fibers with the resin composition, and a composite material obtained by molding the intermediate material.
［従来の技術］
炭素繊維、ガラス繊維等を補強材とする複合材料はゴル
フシャフト、釣竿、テニスラケット等のスポーツ・レジ
ャー用品、航空機、一般産業資材等に使用されている。[Prior Art] Composite materials using carbon fibers, glass fibers, etc. as reinforcing materials are used in sports and leisure goods such as golf shafts, fishing rods, and tennis rackets, aircraft, and general industrial materials.
さらに、近年においては、かかる複合材料か宇宙衛星や
その部品に使用されることか多くなってきた。Furthermore, in recent years, such composite materials have been increasingly used in space satellites and their parts.
［発明が解決しようとする課題〕
しかし、宇宙環境下に、この複合材料が使用された場合
、特に熱サイクル、すなわち高温下あるいは低温下に材
料が順次暴露されたときに複合材料のマトリックス樹脂
にクラックが発生することがある。これは複合材料の劣
化を意味し、この熱サイクルに強い樹脂の開発が望まれ
ている。[Problem to be Solved by the Invention] However, when this composite material is used in a space environment, the matrix resin of the composite material may be damaged, especially when the material is exposed to thermal cycles, that is, sequential exposure to high or low temperatures. Cracks may occur. This means that the composite material deteriorates, and there is a desire to develop a resin that is resistant to this thermal cycle.
本発明者らは、こういった問題に対して検討した結果、
本発明に至った。As a result of considering these problems, the inventors found that
This led to the present invention.
［課題を解決するための手段］
本発明は、（Ａ）エポキシ樹脂、（Ｂ）ＭＢＳ樹脂およ
び（Ｃ）硬化剤を構成成分として含有する複合材料用樹
脂組成物に関する。[Means for Solving the Problems] The present invention relates to a resin composition for a composite material containing (A) an epoxy resin, (B) an MBS resin, and (C) a curing agent as constituent components.
また本発明は前記樹脂組成物を補強繊維に含浸して得ら
れる複合材料用中間材および該中間材を成形して得られ
る複合材料に関する。The present invention also relates to an intermediate material for a composite material obtained by impregnating reinforcing fibers with the resin composition, and a composite material obtained by molding the intermediate material.
本発明に用いられるエポキシ樹脂としては、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、フェノールノボラック型エポキシ樹脂、タレゾール
ノボラック型エポキシ樹脂、グリシジルアミン型エポキ
シ樹脂、脂環式エポキシ樹脂、グリシジルアミン型エポ
キシ樹脂、トリス（グリシジルエーテルフェニル）メタ
ン等の各種エポキシ樹脂を用いることができ、またこれ
らの２種以上のエポキシ樹脂の混合物を用いることがで
きる。Epoxy resins used in the present invention include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, Talezol novolac epoxy resin, glycidylamine epoxy resin, alicyclic epoxy resin, and glycidylamine type epoxy resin. Various epoxy resins such as epoxy resin and tris(glycidyl ether phenyl)methane can be used, and mixtures of two or more of these epoxy resins can also be used.
ビスフェノールＡ型エポキシ樹脂としては、エピコート
８２８、エピコート ８３４、エピコート ８２７、エ
ピコート １００１ 、エピコート １００２ 、エピ
コート１００４、エピコート １００７ エピコー
ト ＬＯＯ９（油化シェルエポキシ社製）、アラルダイ
トＣＹ２Ｏ５、ＣＹ２３０、ＣＹ２３２、ＣＹ２２１、
ＧＹ２５７、ＧＹ２５２、ＧＹ２５５、ＧＹ２５０、Ｇ
Ｙ２６０、ＧＹ２８０、アラルダイト ８０７１ 、ア
ラルダイト ７０７１、アラルダイト ７０７２ （
チバ・ガイギー社製）、ダウエポキシＤＥＲ３３１、Ｄ
ＥＲ３３２、ＤＥＲｆ３Ｂ２、ＤＥＲ６６３Ｕ、 ＤＥ
Ｒ６６２Ｕ （ダウケミカル社製） エピクロン ８４
０．８５０．８５５．８６０、ｌ０５０、３０５０、４
０５０、７０５０ （大日本インキ化学工業社製）
エポトートＹＤ−１１５、ＹＤ−１１５ＣＡ、 ＹＤ−
１１７、ＹＤ−１２１、ＹＤ−１２７、ＹＤ−１２８、
ＹＤ−１２８ＣＡ、 ＹＤ−１２８Ｓ、 ＹＩ）−１３
４、ＹＤ ＱＵＩＺＳＹＤ−０１１、ＹＤ−０１２、
ＹＤ−０１４、ＹＤ−０１４ＥＳ、 ＹＤ−０１７、Ｙ
Ｄ０１９、ＹＤ−０２０、ＹＤ−００２（東部化成社
製）等が挙げられる。Bisphenol A type epoxy resins include Epicote 828, Epicote 834, Epicote 827, Epicote 1001, Epicote 1002, Epicote 1004, Epicote 1007, Epicote LOO9 (manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite CY2O5, CY230, CY232, CY221,
GY257, GY252, GY255, GY250, G
Y260, GY280, Araldite 8071, Araldite 7071, Araldite 7072 (
Ciba Geigy), Dowepoxy DER331, D
ER332, DERf3B2, DER663U, DE
R662U (manufactured by Dow Chemical Company) Epicron 84
0.850.855.860, l050, 3050, 4
050, 7050 (manufactured by Dainippon Ink and Chemicals)
Epotote YD-115, YD-115CA, YD-
117, YD-121, YD-127, YD-128,
YD-128CA, YD-128S, YI)-13
4, YD QUIZSYD-011, YD-012,
YD-014, YD-014ES, YD-017, Y
Examples include D019, YD-020, YD-002 (manufactured by Tobu Kasei Co., Ltd.).
ビスフェノールＦ型エポキシ樹脂としては、ＹＤＦ−１
７０（東部化成社製）等が挙げられる。As bisphenol F type epoxy resin, YDF-1
70 (manufactured by Tobu Kasei Co., Ltd.).
フェノールノボラック型エポキシ樹脂としては、エピコ
ート ｌ５２、エピコート ｌ５４（油化シェルエポキ
シ社製）、アラルダイトＥＰＮ １１３８ 、ＥＰＮ
１１３９ （チバ・ガイギー社製）、ダウエポキシ
ＤＥＮ ４３１． ＤＥＮ ４３８、ＤＥＮ４３９（
ダウケミカル社製） ＥＰＰＮ２０１（日本化薬社製
）、エビクロンＮ７４０（大日本インキ化学工業社製）
、エポトートＹＤＰＮ８３ｇ（東部化成社製）、ＴＡＣ
ＴＩＸ７８５（ダウ・ケミカル日本社製）等が挙げられ
る。Examples of phenol novolac type epoxy resins include Epicort 152, Epicort 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite EPN 1138, and EPN.
1139 (manufactured by Ciba Geigy), Dowepoxy DEN 431. DEN438, DEN439 (
EPPN201 (manufactured by Nippon Kayaku Co., Ltd.), Evicron N740 (manufactured by Dainippon Ink and Chemicals Co., Ltd.)
, Epotote YDPN 83g (manufactured by Tobu Kasei Co., Ltd.), TAC
Examples include TIX785 (manufactured by Dow Chemical Japan Co., Ltd.).
クレゾールノボラック型エポキシ樹脂としては、ＥＣＮ
１２８０ 、ＥＣＮ １２９９ （チバ・ガイギ
ー社製） 、ＥＯＣＮ １０２（Ｂ本化薬社製） 、Ｙ
ＤＣＮ７０１．７０２．７０３．７ｏ４（東部化成社製
）等が挙げられる。As a cresol novolac type epoxy resin, ECN
1280, ECN 1299 (manufactured by Ciba-Geigy), EOCN 102 (manufactured by B Honkayaku), Y
Examples include DCN701.702.703.7o4 (manufactured by Tobu Kasei Co., Ltd.).
グリシジルアミン型エポキシ樹脂としては、アラルダイ
トＭＹ７２０（チバ・ガイギー社製）、エボトートＹＨ
４３４（東部化成社製） 、Ｅ ＬＭ １２０゜ＥＬＭ
４３４（住友化学工業社製） ＰＧＡ−Ｘ（三菱ガス
化学社製）等を例示することができる。Examples of glycidylamine type epoxy resins include Araldite MY720 (manufactured by Ciba Geigy) and Evotote YH.
434 (manufactured by Tobu Kasei Co., Ltd.), ELM 120°ELM
434 (manufactured by Sumitomo Chemical Co., Ltd.), PGA-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.
脂環式エポキシ樹脂としては、アラルダイトＣＹ−１７
９、ＣＹ−１７８、ＣＹ−１８２、ＣＹ−１８３（チハ
・ガイギー社製）等がある。As the alicyclic epoxy resin, Araldite CY-17
9, CY-178, CY-182, CY-183 (manufactured by Chiha Geigy), etc.
本発明において用いるＭＢＳ樹脂とは、ブタジェン、ス
チレンおよびメチルメタクリレートの共重合体である。The MBS resin used in the present invention is a copolymer of butadiene, styrene and methyl methacrylate.
このＭＢＳ樹脂は、鐘淵化学■、兵力化学−１電気化学
銖、三菱レイヨン■、日本合成ゴム■、日本ゼオン■、
宇部サイフン■より上市されており、いずれの製品も使
用可能である。This MBS resin is manufactured by Kanebuchi Chemical ■, Hyoriki Kagaku-1 Electrochemical Coating, Mitsubishi Rayon ■, Nippon Synthetic Rubber ■, Nippon Zeon ■,
It is marketed by Ube Saifun ■, and both products can be used.
ＭＢＳ樹脂の製法は特に限定されないか、−膜内にはラ
テックス状態にあるスチレン・ブタジェンゴム、ポリブ
タジェンゴム等にメチルメタクリレートとスチレンを主
成分とするモノマーを重合して製造される。The manufacturing method of MBS resin is not particularly limited; - MBS resin is manufactured by polymerizing monomers containing methyl methacrylate and styrene as main components to styrene-butadiene rubber, polybutadiene rubber, etc. in a latex state in the membrane.
ＭＢＳ樹脂はエポキシ樹脂１００重量部に対し１〜５０
重量部、好ましくは１〜３０重量部、さらに好ましくは
２〜２０重量部用いられる。MBS resin is 1 to 50 parts by weight per 100 parts by weight of epoxy resin.
Parts by weight are used, preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight.
配合量が１重量部よりも少ないと複合材料としたときの
耐熱サイクルの改良に効果がなく、また５０重量部より
も多いと樹脂組成物の粘度が高くなり補強繊維に含浸さ
せるのが困難となる。If the amount is less than 1 part by weight, it will not be effective in improving the heat cycle resistance of the composite material, and if it is more than 50 parts by weight, the viscosity of the resin composition will become high and it will be difficult to impregnate reinforcing fibers. Become.
本発明において前記成分（Ａ）および（Ｂ）に、硬化剤
（Ｃ）が配合される。配合割合は成分（Ａ）および成分
（Ｂ）の全量１００重量部に対し、成分（Ｃ）は１０〜
８０重量部、好ましくは３０〜６０重量部が用いられる
。In the present invention, a curing agent (C) is blended with the components (A) and (B). The blending ratio is 10 to 10 parts by weight of component (C) to 100 parts by weight of the total amount of component (A) and component (B).
80 parts by weight are used, preferably 30 to 60 parts by weight.
硬化剤としてはジアミノジフェニルスルホン、ジシアン
ジアミドなどが用いられる。As the curing agent, diaminodiphenylsulfone, dicyandiamide, etc. are used.
ジアミノジフェニルスルポンとして、３．３’−ジアミ
ノジフェニルスルホン、４，４°−ジアミノジフェニル
スルホンのいずれも好ましく用いることかできる。As the diaminodiphenylsulfone, either 3,3′-diaminodiphenylsulfone or 4,4°-diaminodiphenylsulfone can be preferably used.
ジシアンジアミドを用いるときは、硬化促進剤として３
−フェニル−１，１−ジメチルウレア、３ｐ−クロロフ
ェニル−１，１−ジメチルウレア、３− （３，４−ジ
クロロフェニル） −１，，１−ジメチルウレア等を併
用するのが好ましい。When using dicyandiamide, 3
-Phenyl-1,1-dimethylurea, 3p-chlorophenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,,1-dimethylurea, etc. are preferably used in combination.
本発明における硬化剤としては、ジアミノジフェニルス
ルホンが特に好ましい。Diaminodiphenylsulfone is particularly preferred as the curing agent in the present invention.
本発明においては前記成分（Ａ） 、 （Ｂ）および（
Ｃ）を含有する樹脂組成物を補強繊維に含浸させ複合材
料用中間材（プリプレグ）とする。In the present invention, the components (A), (B) and (
A reinforcing fiber is impregnated with a resin composition containing C) to obtain an intermediate material for composite material (prepreg).
補強繊維としては特に限定されず複合材料の強化繊維と
して用いられるすべての繊維を用いることができる。例
えばガラス繊維、炭素繊維、アラミド繊維等である。The reinforcing fibers are not particularly limited, and all fibers used as reinforcing fibers for composite materials can be used. For example, glass fiber, carbon fiber, aramid fiber, etc.
補強繊維に本発明の樹脂組成物を含浸させる方法は特に
限定されず公知の方法か用いられる。例えば、樹脂組成
物を溶媒に溶解した溶液中に補強繊維を浸漬した後、溶
媒を除去する溶液法、樹脂組成物を通常６０〜９０℃程
度に加温して補強繊維に含浸させるいわゆるホットメル
ト法等のいずれの方法も採用できる。The method of impregnating the reinforcing fibers with the resin composition of the present invention is not particularly limited, and any known method may be used. For example, a solution method in which reinforcing fibers are immersed in a solution of a resin composition dissolved in a solvent and then the solvent is removed, and a so-called hot melt method in which the reinforcing fibers are impregnated with a resin composition heated to usually about 60 to 90°C. Any method such as the law can be adopted.
溶液法の場合、用いる溶媒としてはアセトン、メチルエ
チルケトン、メタノール、エタノール、ジメチルホルム
アミド等の各種溶剤を用いることができ、またこれらを
混合して用いることもてきる。In the case of the solution method, various solvents such as acetone, methyl ethyl ketone, methanol, ethanol, and dimethylformamide can be used as the solvent, and a mixture of these can also be used.
このようにして製造された中間材の樹脂組成物の含量は
補強繊維と樹脂組成物の総量に対して通常２５〜５０重
量％、好ましくは３０〜４５重量％である。The content of the resin composition in the intermediate material thus produced is usually 25 to 50% by weight, preferably 30 to 45% by weight, based on the total amount of reinforcing fibers and resin composition.
中間材は最終的に複合材料に成形される。例えば中間材
を積層して、オートクレーブ中または加圧プレス等によ
り通常１５０〜２００℃で１〜３時間処理することによ
り、樹脂組成物を加熱硬化させることにより複合材料と
する。The intermediate material is finally formed into a composite material. For example, intermediate materials are laminated and treated in an autoclave or under pressure at a temperature of usually 150 to 200° C. for 1 to 3 hours to heat-cure the resin composition to obtain a composite material.
［発明の効果コ
本発明の複合材料は低温下および高温下の熱サイクルに
暴露した場合において、クラックの発生を著しく抑制す
ることができる。[Effects of the Invention] The composite material of the present invention can significantly suppress the occurrence of cracks when exposed to thermal cycles at low and high temperatures.
［実施例］
以下に実施例を挙げ本発明を具体的に説明するが、本発
明はこれらに制限されるものではない。[Examples] The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.
実施例１
引張強さ ３５（［ｇ／ ｍ ２ 引張弾性率４０
ｔｏｎ／＃２を有する炭素繊維を、エポキシ樹脂として
ビスフェノールＡ型エポキシ樹脂（商品名エピコート
８２８、エポキシ当ｊｌ １９０） ３に’！ （３
０重量部）、Ｎ、Ｎ、Ｎ’ 、Ｎ’ −テトラグリシジ
ルジアミノジフェニルメタン（商品名ＹＨ４３４、エポ
キシ当量１２０） ７Ｋｇ （７０重量部）、ＭＢＳ
樹脂（兵力化学工業■製、商品名Ｂ Ｔ Ａ −７３１
） ｌｏｙ （１０重量部）４．４°−ジアミノジフェ
ニルスルホン４．２８９ （４２重量部）、三フッ化ホ
ウ素モノエチルアミン ｔｏｏ ｇを三本ロールを用い
て均一に混合したのち、この樹脂組成物に含浸して一方
向プリブレグを得た。Example 1 Tensile strength 35 ([g/m 2 Tensile modulus 40
ton/#2 of bisphenol A type epoxy resin (trade name Epicote) as an epoxy resin.
828, epoxy hit jl 190) to 3'! (3
0 parts by weight), N, N, N', N'-tetraglycidyldiaminodiphenylmethane (trade name YH434, epoxy equivalent weight 120) 7Kg (70 parts by weight), MBS
Resin (manufactured by Hyoriki Kagaku Kogyo ■, product name BTA-731
) loy (10 parts by weight) 4.4°-diaminodiphenylsulfone 4.289 (42 parts by weight) and boron trifluoride monoethylamine too g were uniformly mixed using a triple roll, and then added to this resin composition. A unidirectional pre-reg was obtained by impregnation.
このプリプレグを［０’ ／±４５°／９０°］２．に
積層し、オートクレーブを使い、１８０℃、２時間で成
形して多方向コンポジットを得た。このコンポジットを
１５０℃、 １時間〜−２００℃、 １時間の熱サイク
ルを１００回繰り返したのち、コンポジットを切断して
ＳＥＭ（走査電子顕微鏡）観察をした。切断面には熱サ
イクルテストによるクラックの発生は殆んど認められな
かった。Cut this prepreg into [0'/±45°/90°]2. were laminated and molded in an autoclave at 180°C for 2 hours to obtain a multidirectional composite. This composite was subjected to a thermal cycle of 150° C. for 1 hour to −200° C. for 1 hour 100 times, and then the composite was cut and observed using a scanning electron microscope (SEM). Almost no cracks were observed on the cut surface during the thermal cycle test.
比較例Ｉ
ＭＢＳ樹脂を用いない以外は実施例１と同様の方法でプ
リプレグ多方向コンポジットを得た。Comparative Example I A prepreg multidirectional composite was obtained in the same manner as in Example 1 except that MBS resin was not used.
このコンポジットを実施例１と同し熱サイクルテストを
行ないその切断面のＳＥＭ観察を行なったところ、多数
のクラックが認められた。This composite was subjected to a thermal cycle test in the same manner as in Example 1, and its cut surface was observed by SEM, and many cracks were observed.
実施例２
実施例１と同じ炭素繊維を、エポキシ樹脂としてビスフ
ェノールＦ型エポキシ樹脂（商品名工ポトートＹＤＦ１
７０、エポキシ当量１６７） ２／（ｇ（２０重量部
）、フェノールノボラック型エポキシ樹脂（商品名エピ
コート １５４、エポキシ当ｊｌ １７７） ８に’
ｊＣ８０重量部）、ＭＢＳ樹脂（兵力化学工業■製、商
品名Ｂ Ｔ Ａ −７５１） １．５酌（１５重量部）
、３．３ジアミノジフェニルスルホン３．４５Ａ９
（３４，５重量部）を添加した樹脂組成物に含浸し、実
施例１と同様にして多方向コンポジットを得た。Example 2 The same carbon fiber as in Example 1 was used as an epoxy resin, a bisphenol F type epoxy resin (trade name: Potote YDF1).
70, epoxy equivalent 167) 2/(g (20 parts by weight), phenol novolac type epoxy resin (trade name Epicote 154, epoxy equivalent jl 177) 8'
1.5 cup (15 parts by weight)
, 3.3 diaminodiphenylsulfone 3.45A9
(34.5 parts by weight) was impregnated into a resin composition to obtain a multidirectional composite in the same manner as in Example 1.
実施例１と同様の方法で熱サイクルテストを行なったの
ち、そのコンポジットを切断してＳＥＭ観察を行なった
。クラックの発生は殆ど認められなかった。After conducting a thermal cycle test in the same manner as in Example 1, the composite was cut and subjected to SEM observation. Almost no cracks were observed.
比較例２
Ｍ Ｂ Ｓ樹脂を用いない以外は実施例２と同様の方法
でプリプレグおよび多方向コンポジットを得た。Comparative Example 2 A prepreg and a multidirectional composite were obtained in the same manner as in Example 2 except that the MBS resin was not used.
このコンポジットを実施例１と同し熱サイクルテストを
行ない、その後このコンポジットを切断してＳＥＭ観察
を行なったところ、多数のクラックが発生していた。This composite was subjected to a thermal cycle test in the same manner as in Example 1, and then the composite was cut and subjected to SEM observation, which revealed that many cracks had occurred.
Claims (1)
）硬化剤を構成成分として含有する複合材料用樹脂組成
物。 ２、請求項第１項記載の樹脂組成物を補強繊維に含浸し
て得られる複合材料用中間材。 ３、請求項第２項記載の中間材を成形して得られる複合
材料。[Claims] 1. (A) epoxy resin, (B) MBS resin and (C
) A resin composition for composite materials containing a curing agent as a component. 2. An intermediate material for a composite material obtained by impregnating reinforcing fibers with the resin composition according to claim 1. 3. A composite material obtained by molding the intermediate material according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21440190A JP3066907B2 (en) | 1990-08-15 | 1990-08-15 | Resin composition for composite material, intermediate material and composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21440190A JP3066907B2 (en) | 1990-08-15 | 1990-08-15 | Resin composition for composite material, intermediate material and composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0496921A true JPH0496921A (en) | 1992-03-30 |
| JP3066907B2 JP3066907B2 (en) | 2000-07-17 |
Family
ID=16655183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21440190A Expired - Lifetime JP3066907B2 (en) | 1990-08-15 | 1990-08-15 | Resin composition for composite material, intermediate material and composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3066907B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996004333A1 (en) * | 1994-08-04 | 1996-02-15 | Ici Composites Inc. | Composite material |
| JPH08199044A (en) * | 1995-01-27 | 1996-08-06 | Hitachi Cable Ltd | Epoxy resin composition for equipment insulated with sulfur hexafluoride gas |
| US6063839A (en) * | 1995-05-09 | 2000-05-16 | Toray Industries, Inc. | Prepreg of reinforcing fibers, epoxy resins, crosslinked rubber particles and curing agent |
-
1990
- 1990-08-15 JP JP21440190A patent/JP3066907B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996004333A1 (en) * | 1994-08-04 | 1996-02-15 | Ici Composites Inc. | Composite material |
| JPH08199044A (en) * | 1995-01-27 | 1996-08-06 | Hitachi Cable Ltd | Epoxy resin composition for equipment insulated with sulfur hexafluoride gas |
| US6063839A (en) * | 1995-05-09 | 2000-05-16 | Toray Industries, Inc. | Prepreg of reinforcing fibers, epoxy resins, crosslinked rubber particles and curing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3066907B2 (en) | 2000-07-17 |
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