JPH04370140A - Resin composition for composite material, intermediate material and composite material - Google Patents
Resin composition for composite material, intermediate material and composite materialInfo
- Publication number
- JPH04370140A JPH04370140A JP17191691A JP17191691A JPH04370140A JP H04370140 A JPH04370140 A JP H04370140A JP 17191691 A JP17191691 A JP 17191691A JP 17191691 A JP17191691 A JP 17191691A JP H04370140 A JPH04370140 A JP H04370140A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- composite material
- manufactured
- composite
- intermediate material
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 18
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 18
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 14
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 9
- 239000004945 silicone rubber Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims abstract description 5
- 239000000806 elastomer Substances 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 3
- 238000000465 moulding Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 229920003319 Araldite® Polymers 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 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 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004593 Epoxy Substances 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
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 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 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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 3
- 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
- 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
- 239000002245 particle Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 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 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 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 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 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 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
- 101001018878 Mus musculus Macrophage migration inhibitory factor Proteins 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
- 239000006185 dispersion Substances 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
- 239000000835 fiber Substances 0.000 description 1
- -1 glycidyl ester Chemical class 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】0001
【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。BACKGROUND OF THE INVENTION 1. Field of the Invention 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.
【０００２】0002
【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。2. Description of the Related 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.
【０００３】さらに、近年においては、かかる複合材料
が宇宙衛星やその部品に使用されることが多くなってき
た。Furthermore, in recent years, such composite materials have been increasingly used for space satellites and their parts.
【０００４】0004
【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。[Problems to be Solved by the Invention] However, when this composite material is used in a space environment, the matrix resin of the composite material is 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.
【０００５】本発明は熱サイクルに強い樹脂組成物およ
びそれを補強繊維に含浸して得られる中間材、並びに該
中間材を成形して得られる複合材料を提供することを目
的とする。The object of the present invention is to provide a resin composition that is resistant to thermal cycles, an intermediate material obtained by impregnating reinforcing fibers with the resin composition, and a composite material obtained by molding the intermediate material.
【０００６】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。The present inventors have studied these problems and have arrived at the present invention.
【０００７】[0007]
【課題を解決するための手段】本発明は（Ａ）エポキシ
樹脂、（Ｂ）シリコーンゴム弾性体および（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。SUMMARY OF THE INVENTION The present invention relates to a resin composition for composite materials containing (A) an epoxy resin, (B) a silicone rubber elastomer, and (C) a curing agent as constituent components.
【０００８】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.
【０００９】本発明に用いられるエポキシ樹脂（以下、
成分（Ａ）という）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、ク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、グリシジルエステル型エポキシ樹脂、
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 resin used in the present invention (hereinafter referred to as
Component (A)) includes bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, glycidylamine epoxy resin, alicyclic epoxy resin, and glycidyl ester epoxy resin. ,
Various epoxy resins such as tris(glycidyl ether phenyl)methane can be used, and these 2
Mixtures of more than one type of epoxy resin can be used.
【００１０】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８
２７、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１０
０９（油化シェルエポキシ社製）、アラルダイトＣＹ２
０５、ＣＹ２３０、ＣＹ２３２、ＣＹ２２１、ＧＹ２５
７、ＧＹ２５２、ＧＹ２５５、ＧＹ２５０、ＧＹ２６０
、ＧＹ２８０、アラルダイト６０７１、アラルダイト７
０７１、アラルダイト７０７２（チバ・ガイギー社製）
、ダウエポキシＤＥＲ３３１、ＤＥＲ３３２、ＤＥＲ６
６２、ＤＥＲ６６３Ｕ、ＤＥＲ６６２Ｕ（ダウケミカル
社製）、エピクロン８４０、８５０、８５５、８６０、
１０５０、３０５０、４０５０、７０５０（大日本イン
キ化学工業社製）、エポトートＹＤ−１１５、ＹＤ−１
１５ＣＡ、ＹＤ−１１７、ＹＤ−１２１、ＹＤ−１２７
、ＹＤ−１２８、ＹＤ−１２８ＣＡ、ＹＤ−１２８Ｓ、
ＹＤ−１３４、ＹＤ００１Ｚ、ＹＤ−０１１、ＹＤ−０
１２、ＹＤ−０１４、ＹＤ−０１４ＥＳ、ＹＤ−０１７
、ＹＤ−０１９、ＹＤ−０２０、ＹＤ−００２（東都化
成社製）等が挙げられる。[0010] As the bisphenol A type epoxy resin, Epicote 828, Epicote 834, Epicote 8
27, Epicote 1001, Epicote 1002, Epicote 1004, Epicote 1007, Epicote 10
09 (manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite CY2
05, CY230, CY232, CY221, GY25
7, GY252, GY255, GY250, GY260
, GY280, Araldite 6071, Araldite 7
071, Araldite 7072 (manufactured by Ciba Geigy)
, Dowepoxy DER331, DER332, DER6
62, DER663U, DER662U (manufactured by Dow Chemical Company), Epicron 840, 850, 855, 860,
1050, 3050, 4050, 7050 (manufactured by Dainippon Ink and Chemicals), Epotote YD-115, YD-1
15CA, YD-117, YD-121, YD-127
, YD-128, YD-128CA, YD-128S,
YD-134, YD001Z, YD-011, YD-0
12, YD-014, YD-014ES, YD-017
, YD-019, YD-020, YD-002 (manufactured by Toto Kasei Co., Ltd.), and the like.
【００１１】ビスフェノールＦ型エポキシ樹脂としては
、ＹＤＦ−１７０（東都化成社製）等が挙げられる。[0011] Examples of the bisphenol F type epoxy resin include YDF-170 (manufactured by Toto Kasei Co., Ltd.).
【００１２】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１５２、エピコート１５４（油化シェ
ルエポキシ社製）、アラルダイトＥＰＮ１１３８、ＥＰ
Ｎ１１３９（チバ・ガイギー社製）、ダウエポキシＤＥ
Ｎ４３１、ＤＥＮ４３８、ＤＥＮ４３９（ダウケミカル
社製）、ＥＰＰＮ２０１（日本化薬社製）、エピクロン
Ｎ７４０（大日本インキ化学工業社製）、エポトートＹ
ＤＰＮ６３８（東都化成社製）、ＴＡＣＴＩＸ７８５（
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 Epicote 152, Epicote 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite EPN1138, EP
N1139 (manufactured by Ciba Geigy), Dowepoxy DE
N431, DEN438, DEN439 (manufactured by Dow Chemical Co.), EPPN201 (manufactured by Nippon Kayaku Co., Ltd.), Epicron N740 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Epotote Y
DPN638 (manufactured by Toto Kasei Co., Ltd.), TACTIX785 (
(manufactured by Dow Chemical Japan), etc.
【００１３】クレゾールノボラック型エポキシ樹脂とし
ては、ＥＣＮ１２８０、ＥＣＮ１２９９（チバ・ガイギ
ー社製）、ＥＯＣＮ１０２（日本化薬社製）、ＹＤＣＮ
７０１、７０２、７０３、７０４（東都化成社製）等が
挙げられる。[0013] Cresol novolak type epoxy resins include ECN1280, ECN1299 (manufactured by Ciba-Geigy), EOCN102 (manufactured by Nippon Kayaku Co., Ltd.), and YDCN.
701, 702, 703, 704 (manufactured by Toto Kasei Co., Ltd.), and the like.
【００１４】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
ポトートＹＨ４３４（東都化成社製）、ＥＬＭ１２０、
ＥＬＭ４３４（住友化学工業社製）、ＴＥＴＲＡＤ−Ｃ
，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), Epotote YH434 (manufactured by Toto Kasei), ELM120,
ELM434 (manufactured by Sumitomo Chemical Co., Ltd.), TETRAD-C
, X (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
【００１５】脂環式エポキシ樹脂としては、アラルダイ
トＣＹ−１７９、ＣＹ−１７８、ＣＹ−１８２、ＣＹ−
１８３チバ・ガイギー社製）等がある。As the alicyclic epoxy resin, Araldite CY-179, CY-178, CY-182, CY-
183 (manufactured by Ciba-Geigy), etc.
【００１６】トリス（グリシジルエーテルフェニル）メ
タンとしては、ＴＡＣＴＩＸ７４２（ダウケミカル日本
社製）が挙げられる。[0016] As the tris(glycidyl ether phenyl)methane, TACTIX742 (manufactured by Dow Chemical Japan Co., Ltd.) can be mentioned.
【００１７】本発明において用いるシリコーンゴム弾性
体（以下、成分（Ｂ）という）とは、平均粒径が１〜２
０μｍであり、球状に微粒子化したものである。平均粒
径が２０μｍより大きくなると硬化後の樹脂中における
分散が不均一になる。The silicone rubber elastic body (hereinafter referred to as component (B)) used in the present invention has an average particle size of 1 to 2.
It has a particle size of 0 μm and is made into spherical particles. If the average particle size is larger than 20 μm, the dispersion in the cured resin will become non-uniform.
【００１８】本発明で使用できるシリコーン弾性体の具
体例としては、トレフィルＥシリーズ（東レダウコーニ
ングシリコーン社製）が挙げられる。A specific example of the silicone elastomer that can be used in the present invention is the Trefil E series (manufactured by Dow Corning Toray Silicone Co., Ltd.).
【００１９】成分（Ｂ）は成分（Ａ）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。Component (B) is used in an amount of 1 to 50 parts by weight, preferably 1 to 30 parts by weight, and more preferably 2 to 20 parts by weight, based on 100 parts by weight of component (A).
【００２０】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５
０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。[0020] If the blending amount is less than 1 part by weight, it will not be effective in improving the heat resistance cycle when made into a composite material, and
When the amount is more than 0 parts by weight, the viscosity of the resin composition increases, making it difficult to impregnate reinforcing fibers.
【００２１】本発明において前記成分（Ａ）および（Ｂ
）に、硬化剤（以下、成分（Ｃ）という）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。[0021] In the present invention, the components (A) and (B)
) is blended with a curing agent (hereinafter referred to as component (C)). The blending ratio is the total amount of component (A) and component (B): 100
Component (C) is used in an amount of 10 to 80 parts by weight, preferably 30 to 60 parts by weight.
【００２２】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.
【００２３】ジアミノジフェニルスルホンとして、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が
できる。As diaminodiphenylsulfone, 3,
Either 3'-diaminodiphenylsulfone or 4,4'-diaminodiphenylsulfone can be preferably used.
【００２４】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、３
−ｐ−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, 3-phenyl-1,1-dimethylurea,
-p-chlorophenyl-1,1-dimethylurea, 3-
It is preferable to use (3,4-dichlorophenyl)-1,1-dimethylurea or the like in combination.
【００２５】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.
【００２６】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 above components (A) and (B)
A reinforcing fiber is impregnated with a resin composition containing (C) and an intermediate material (prepreg) for a composite material.
【００２７】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.
【００２８】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が用いられる。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６
０〜９０℃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 for 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 in which a resin composition is dissolved in a solvent and then the solvent is removed;
Any method such as the so-called hot-melt method in which reinforcing fibers are impregnated by heating to about 0 to 90° C. can be adopted.
【００２９】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できる。In the case of the solution method, various solvents such as acetone, methyl ethyl ketone, methanol, ethanol, and dimethylformamide can be used.
Moreover, these can also be used as a mixture.
【００３０】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.
【００３１】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。[0031] 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.
【００３２】[0032]
【発明の効果】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.
【００３３】[0033]
【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 explained with reference to Examples below, but the present invention is not limited thereto.
【００３４】実施例１
引張強さ３５０Ｋｇ／ｍｍ２、引張弾性率４０ｔｏｎ／
ｍｍ２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、
エポキシ当量１９０）３Ｋｇ（３０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量部）、シリコーンゴム弾性体（東レダウコーニン
グシリコーン社製、商品名トレフィルＥ５０１）１Ｋｇ
（１０重量部）４，４′−ジアミノジフェニルスルホン
４．２Ｋｇ（４２重量部）、三フッ化ホウ素モノエチル
アミン１００ｇ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プレグを得た
。Example 1 Tensile strength 350Kg/mm2, tensile modulus 40ton/
Carbon fibers having a diameter of
Epoxy equivalent 190) 3Kg (30 parts by weight), N,N,
N',N'-tetraglycidyldiaminodiphenylmethane (trade name YH434, epoxy equivalent 120) 7Kg (
70 parts), 1 kg of silicone rubber elastic body (manufactured by Toray Dow Corning Silicone Co., Ltd., trade name: Torefil E501)
(10 parts by weight) 4.2 kg (42 parts by weight) of 4,4'-diaminodiphenylsulfone and 100 g of boron trifluoride monoethylamine were mixed uniformly using a triple roll, and then impregnated into this resin composition. A unidirectional prepreg was obtained.
【００３５】このプリプレグを［０°／±４５°／９０
°］２Ｓ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。[0035] This prepreg is [0°/±45°/90
°] Laminated on 2S, using autoclave, 180℃,
A multidirectional composite was obtained by molding in 2 hours. After this composite was subjected to a thermal cycle of 150° C. for 1 hour to -200° C. for 1 hour 100 times, 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.
【００３６】比較例１
シリコーンゴム弾性体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 1 A prepreg multidirectional composite was obtained in the same manner as in Example 1 except that the silicone rubber elastomer was not used.
【００３７】このコンポジットを実施例１と同じ熱サイ
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。When this composite was subjected to the same thermal cycle test as in Example 1 and the cut surface was observed by SEM, many cracks were observed.
【００３８】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（商品名エポトートＹＤＦ１
７０、エポキシ当量１６７）２Ｋｇ（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、エポキシ当量１７７）８Ｋｇ（８０重量部）、
シリコーンゴム弾性体（東レダウコーニングシリコーン
社製、商品名トレフィルＥ６０１）１．５Ｋｇ（１５重
量部）、３，３′−ジアミノジフェニルスルホン３．４
５Ｋｇ（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, using bisphenol F type epoxy resin (trade name Epotote YDF1).
70, epoxy equivalent 167) 2Kg (20 parts by weight), phenol novolac type epoxy resin (trade name Epicote 154, epoxy equivalent 177) 8Kg (80 parts by weight),
Silicone rubber elastic body (manufactured by Dow Corning Toray Silicone Co., Ltd., trade name Torefil E601) 1.5 kg (15 parts by weight), 3,3'-diaminodiphenylsulfone 3.4
A multidirectional composite was obtained in the same manner as in Example 1 by impregnating it with a resin composition to which 5 kg (34.5 parts by weight) had been added.
【００３９】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 carrying out 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.
【００４０】比較例２
シリコーンゴム弾性体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 silicone rubber elastomer was not used.
【００４１】このコンポジットを実施例１と同じ熱サイ
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。[0041] This composite was subjected to the same thermal cycle test as in Example 1, and then the composite was cut and observed under SEM, and many cracks were found.
Claims (3)
ンゴム弾性体および（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。1. A resin composition for a composite material, which contains (A) an epoxy resin, (B) a silicone rubber elastomer, and (C) a curing agent as constituent components.
繊維に含浸して得られる複合材料用中間材。2. An intermediate material for a composite material obtained by impregnating reinforcing fibers with the resin composition according to claim 1.
得られる複合材料。3. A composite material obtained by molding the intermediate material according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17191691A JPH04370140A (en) | 1991-06-18 | 1991-06-18 | Resin composition for composite material, intermediate material and composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17191691A JPH04370140A (en) | 1991-06-18 | 1991-06-18 | Resin composition for composite material, intermediate material and composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04370140A true JPH04370140A (en) | 1992-12-22 |
Family
ID=15932220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17191691A Pending JPH04370140A (en) | 1991-06-18 | 1991-06-18 | Resin composition for composite material, intermediate material and composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04370140A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064983C (en) * | 1994-03-25 | 2001-04-25 | 信越化学工业株式会社 | Silicone rubber/epoxy resin integral composite and method for making |
| JP2005213352A (en) * | 2004-01-29 | 2005-08-11 | Arisawa Mfg Co Ltd | Resin composition for prepreg and prepreg using the same |
-
1991
- 1991-06-18 JP JP17191691A patent/JPH04370140A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064983C (en) * | 1994-03-25 | 2001-04-25 | 信越化学工业株式会社 | Silicone rubber/epoxy resin integral composite and method for making |
| JP2005213352A (en) * | 2004-01-29 | 2005-08-11 | Arisawa Mfg Co Ltd | Resin composition for prepreg and prepreg using the same |
| JP4553595B2 (en) * | 2004-01-29 | 2010-09-29 | 株式会社有沢製作所 | Prepreg resin composition and prepreg using the same |
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