JPS59207919A - Epoxy resin composition of high elongation - Google Patents
Epoxy resin composition of high elongationInfo
- Publication number
- JPS59207919A JPS59207919A JP8331583A JP8331583A JPS59207919A JP S59207919 A JPS59207919 A JP S59207919A JP 8331583 A JP8331583 A JP 8331583A JP 8331583 A JP8331583 A JP 8331583A JP S59207919 A JPS59207919 A JP S59207919A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- component
- resin
- elongation
- weight
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 10
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 9
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 25
- 229920005989 resin Polymers 0.000 abstract description 16
- 239000011347 resin Substances 0.000 abstract description 16
- 239000011159 matrix material Substances 0.000 abstract description 11
- -1 amino- substituted diphenyl sulfone Chemical class 0.000 abstract description 7
- 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 7
- 229920003986 novolac Polymers 0.000 abstract description 6
- 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 abstract description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 abstract description 2
- 229940106691 bisphenol a Drugs 0.000 abstract 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 10
- 239000004917 carbon fiber Substances 0.000 description 10
- 239000012783 reinforcing fiber Substances 0.000 description 10
- 229920003319 Araldite® Polymers 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 230000000052 comparative effect Effects 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
- 230000000704 physical effect Effects 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000126 substance 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 229930003836 cresol Natural products 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
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 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
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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】
本発明は、優れた耐熱性と高伸度性を備えたエポキシ樹
脂組成物に関するものである。更に詳しくは、本組成物
をマトリックス樹脂として高伸度且つ耐熱性のある強化
材繊維と組合せて使用した場合に耐熱性且つ高伸度の複
合材料を１りることのできるエポキシ樹脂組成物に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition having excellent heat resistance and high elongation. More specifically, the present invention relates to an epoxy resin composition that can produce a heat-resistant and high-elongation composite material when the present composition is used as a matrix resin in combination with high-elongation and heat-resistant reinforcing fibers. It is something.
近年、強化材繊維とマトリックス樹脂とからなる複合材
料は、種々の構造部材として多く使用されてきている。In recent years, composite materials made of reinforcing fibers and matrix resins have been widely used as various structural members.
特に炭阜繊維、芳香族ポリアミド等を強化材繊維として
用いた複合材料は、高い比強度、比剛性を利用して航空
機等の構造祠どして多く用いられている。これらの航空
機用複合材料が上記特性の外に更に耐熱性と高伸度とを
兼ね備えたものであれば、複合材料の応用範囲は第二次
構造部材に限定されず、広く第一次構造部材にも応用可
能となり、航空機の軽鎖化は飛躍的に進み省エネルギー
と安全性の面から大きな利点がある。In particular, composite materials using charcoal fibers, aromatic polyamides, etc. as reinforcing fibers are often used for structural shrines of aircraft etc., taking advantage of their high specific strength and specific rigidity. If these composite materials for aircraft have heat resistance and high elongation in addition to the above properties, the range of application of composite materials will not be limited to secondary structural members, but will be widely used in primary structural members. It has also become possible to apply this technology to aircraft, making rapid progress in reducing the weight of aircraft chains, bringing great advantages in terms of energy savings and safety.
この複合材料の強化材繊維としての炭素繊維は、従来伸
度１，０〜１．３％程麿の低伸度のものであったが、近
時伸度が１．５％以上の高伸度炭素繊維が開発されつつ
あり、どのため高伸度の複合材料を提供できることが期
待された。しかしながら複合材料の一方の成分であるマ
トリックス樹脂に耐熱性と高伸度性を兼ね備えたものが
なく、このため高伸度炭素繊維の性質が充分生かされる
ことがなかった。The carbon fiber used as the reinforcing fiber in this composite material has conventionally had a low elongation of about 1.0 to 1.3%, but recently it has become highly elongated with an elongation of 1.5% or more. High-strength carbon fibers are being developed, and it was hoped that they could provide high-strength composite materials. However, there is no matrix resin that is one component of the composite material that has both heat resistance and high elongation, and therefore the properties of high elongation carbon fibers have not been fully utilized.
すなわち、一般に、マトリックス樹脂の耐熱性が優れた
ものは伸度が低く、逆に伸度の高いものは耐熱性が劣る
という関係があり、この両方の要求を同時に満足するこ
とはできなかった。That is, in general, matrix resins with excellent heat resistance have low elongation, and conversely, those with high elongation have poor heat resistance, and it has not been possible to satisfy both of these requirements at the same time.
本発明者らは、高伸度強化材繊維と組合Ｉて使用した場
合に、耐熱性の基準となる１００℃における層間剪断強
麿（ＩＬＳＳ）が７に！＋ ／ｍｍ’以上好ましくは８
に９ ／ｍｍ’以上で且つ伸度が１．５％以上ある耐熱
性と高伸度を併せもつ複合材料を得ることのできるマト
リックス樹脂について検問の結果本発明に至ったもので
ある。The present inventors have found that when used in combination with high elongation reinforcing fibers, the interlaminar shear strength (ILSS) at 100°C, which is the standard for heat resistance, is 7! + /mm' or more preferably 8
The present invention was developed as a result of investigation into a matrix resin that can produce a composite material that has both heat resistance and high elongation, such as 9/mm' or more and an elongation of 1.5% or more.
本発明の樹脂組成物は、高伸度炭素繊維のみならず、通
常しばしば使用されるガラス繊維、芳香族ポリアミド繊
維を強化材とする複合材料用マトリックス樹脂どして有
用である。The resin composition of the present invention is useful not only as a matrix resin for composite materials reinforced with high elongation carbon fibers but also glass fibers and aromatic polyamide fibers, which are commonly used.
すなわち、本発明は、下記〔△〕〜（Ｅ）成分を含み且
つ（Ｂ）成分をエポキシ樹脂との反応物として含むエポ
キシ樹脂組成物である。That is, the present invention is an epoxy resin composition containing the following components [Δ] to (E) and containing component (B) as a reaction product with the epoxy resin.
タジエンーアクリロニトリル共重合体
（Ｃ）ニトリルゴム
（Ｄ）アミノ置換ジフェニルスルボン
（Ｅ）ジシアンジアミド及びその硬化促進剤このような
エポキシ樹脂組成物は、耐熱性と高伸度性とを兼ね備え
たエポキシ樹脂組成物であって、特に、このものを高伸
度の強化材繊維と共に使用して得た複合材料は耐熱性且
つ高伸度の優れた物性を示し、マトリックス材であるエ
ポキシ樹脂の伸度、耐熱性が劣るがゆえに複合ノ
リシジルアミン系エポキシ樹を含むものである。Tadiene-acrylonitrile copolymer (C) Nitrile rubber (D) Amino-substituted diphenyl sulfone (E) Dicyandiamide and its curing accelerator Such an epoxy resin composition is an epoxy resin that has both heat resistance and high elongation. A resin composition, in particular, a composite material obtained by using this composition together with high elongation reinforcing fibers exhibits excellent physical properties such as heat resistance and high elongation, and the elongation of the epoxy resin that is the matrix material is , contains a composite noricidylamine-based epoxy tree because of its poor heat resistance.
（Ａ）成分はこのほかノボラック系エポキシ樹脂、ビス
フェノールＡ系エボギシ樹脂、ウレタン変成ビスフェノ
ールＡ系エポキシ樹脂、脂環式エポキシ樹脂等の単独又
は混合エポキシ樹脂を含んでいてもよい。Component (A) may also contain a single or mixed epoxy resin such as a novolac epoxy resin, a bisphenol A epoxy resin, a urethane-modified bisphenol A epoxy resin, and an alicyclic epoxy resin.
本発明におけるグリシジルアミン系エポキシ樹脂として
は、Ｎ、Ｎ、Ｎ−、Ｎ＝ −テトラグリシジル−ビス
（アミノフェニル〉メタン〔アラルダイトＭ Ｙ −７
２０（チバ・ガイギー社製）、エボトートＹ）−１４３
４（京都化成ネ１製））、Ｎ、Ｎ、 ｏ−トリグリシジ
ルートアミノフェノール〔エボトートＹＤＭ１２０（東
部化成社製）〕、〕Ｎ、Ｎ、０−トリグリシジルー〇ア
ミノフェノールなどがある。The glycidylamine-based epoxy resin in the present invention includes N, N, N-, N=-tetraglycidyl-bis(aminophenyl>methane [Araldite M Y-7
20 (manufactured by Ciba Geigy), Evotote Y)-143
4 (manufactured by Kyoto Kasei Nei 1)), N,N,o-triglycidyl-aminophenol [Evototo YDM120 (manufactured by Tobu Kasei Co., Ltd.)], and N,N,0-triglycidyl-aminophenol.
ノボラック系エポキシ樹脂としてはフェノール・ノボラ
ック系とクレゾール・ノボラック系があり、フェノール
ノボラック系エポキシ樹脂としては、具体的には例えば
、エピコーｈ １５２、エピコート １５４（シェル
化学社製）、アラルダイトＥ Ｐ Ｎ １１３８、Ｅ
Ｐ Ｎ １１３９ （チバ・ガイギー社製）、ダウエポ
キシＤＥＮ４３１、ＤＥＮ４３８、ＤＥＮ４３９、ＸＤ
７８５５（ダウケミカル社製）、ＥＰＰＮ２０１（日本
生薬社製）、■ビクロンＮ７４０（大日本インキ化学工
業社製）等が挙げられる。Novolac epoxy resins include phenol novolak and cresol novolac. Specific examples of phenol novolak epoxy resins include Epicor h 152, Epicor 154 (manufactured by Shell Chemical Co., Ltd.), and Araldite E P N 1138. ,E
P N 1139 (manufactured by Ciba Geigy), Dowepoxy DEN431, DEN438, DEN439, XD
7855 (manufactured by Dow Chemical Co., Ltd.), EPPN201 (manufactured by Nippon Koyaku Co., Ltd.), and ■ Viclon N740 (manufactured by Dainippon Ink and Chemicals Co., Ltd.).
クレゾール・ノボラック系エポキシ樹脂どじてチバ・ガ
イギーＥ ＣＮ １２３５．１２７３．１２８０．１２
９９（ヂバ・ガイギー社製）、ＦＯＣＮ１０２．１０３
．１０４（日本生薬社製）、またビスフェノール△型エ
ポキシ樹脂は公知のものを用いることができ、具体的に
は例えば、エピコート８２８、エビコート８３４、エピ
コート８２７、エピコート１００１、エピコート１００
２、エビコー１へ１００４、エピコート１００７、エピ
コート１００９ （シェル化学社製）、アラルダイトＣ
Ｙ２Ｏ５、ＣＹ２３０、ＣＹ２３２、ＣＹ２２１、ＧＹ
２５７、ＧＹ２５２、ＧＹ２５５、ＧＹ２５０、ＧＹ２
６０、ＧＹ２８０、アラルダイト６０７１、アラルタイ
ト７０７１、アラルダイト７０７２ （チバ・ガイギー
社製）、ダウエポキシＤＥＲ３３１、ＤＥＲ３３２、Ｄ
ＥＲ６６２、ＤＥＲ６６３Ｕ、 ＤＥＲ１３６２１Ｊ
（ダウケミカル社製）、エビクロン８４０．８５０．８
５５．８６０．１０５０．３０５６．４０５０．７０５
０（大日本インキ化学工業社製）、エポ１〜−トＹ［）
−１１５、ｙ Ｄ １１５−ＣΔ、ＹＤ−１１７、”ｙ
’ ［） −１２１、’１’［）、−１２７、Ｙ Ｄ−
１２８、Ｙ Ｄ −１２８ＣＡ 、 Ｙ Ｄ −１２８
Ｓ １Ｙ Ｄ−，１３４、Ｙ Ｄ−００１２、Ｙ Ｄ−
０１１、ＹＤ−０」２、Ｙ Ｄ−０１４、Ｙ Ｄ −０
１４Ｅ Ｓ １Ｙ Ｄ−０１７、ＹＤ−０１９、Ｙ Ｄ
−０２０、Ｙ［） −００２（東部化成社製〉等が挙げ
られる。Cresol/novolak epoxy resin Dojite Ciba Geigy E CN 1235.1273.1280.12
99 (manufactured by Ziba Geigy), FOCN102.103
．． 104 (manufactured by Nippon Koyaku Co., Ltd.), and known bisphenol Δ type epoxy resins can be used, specifically, for example, Epicote 828, Ebicoat 834, Epicote 827, Epicote 1001, Epicote 100.
2. Ebicor 1 to 1004, Epicort 1007, Epicort 1009 (manufactured by Shell Chemical Co., Ltd.), Araldite C
Y2O5, CY230, CY232, CY221, GY
257, GY252, GY255, GY250, GY2
60, GY280, Araldite 6071, Araldite 7071, Araldite 7072 (manufactured by Ciba Geigy), Dowepoxy DER331, DER332, D
ER662, DER663U, DER13621J
(manufactured by Dow Chemical Company), Evicron 840.850.8
55.860.1050.3056.4050.705
0 (manufactured by Dainippon Ink and Chemicals), Epo 1~-t Y [)
-115,y D 115-CΔ,YD-117,”y
' [) -121, '1' [), -127, Y D-
128, YD-128CA, YD-128
S 1Y D-, 134, Y D-0012, Y D-
011,YD-0''2,YD-014,YD-0
14E S 1Y D-017, YD-019, Y D
-020, Y[)-002 (manufactured by Tobu Kasei Co., Ltd.), and the like.
ウレタン変成ビスフェノールＡ系エポキシ樹脂としては
、アデカレジンＥＰ’Ｕ−６、ＥＰ、Ｕ−１０、ＩＥＰ
Ｕ−１５（旭電化社Ｉ！７）等がある。Examples of urethane-modified bisphenol A-based epoxy resins include Adekal Resin EP'U-6, EP, U-10, and IEP.
There are U-15 (Asahi Denkasha I!7), etc.
脂環式エポキシ樹脂としては、アラルダイｌ−ＣＹ−１
７９、ＣＹ−１７８、ＣＹ−１８２、ＣＹ −１８３（
ヂバ・ガイギー社製）等がある。As the alicyclic epoxy resin, Araldai l-CY-1
79, CY-178, CY-182, CY-183 (
(manufactured by Ziba Geigy), etc.
これらエポキシ樹脂は混合して用いるのがよく、特にグ
リシジルアミン系エポキシ樹脂が全エポキシ樹脂中の３
０重量％以上の場合に耐熱性が良好となり、また高伸度
を兼ね備えたものとなる。グリシジルアミン系エポキシ
樹脂、フェノールノボラック系エポキシ樹脂、ビスフェ
ノールＡ系エポキシ樹脂との混合系が好ましい。It is best to use these epoxy resins as a mixture, especially when glycidylamine epoxy resin accounts for 3% of the total epoxy resin.
When the content is 0% by weight or more, heat resistance becomes good and high elongation is achieved. A mixed system with a glycidylamine-based epoxy resin, a phenol novolak-based epoxy resin, and a bisphenol A-based epoxy resin is preferred.
ＣＢ）成分は、両末端にカルボキシル基を有する液状の
ブタジェン−アクリロニトリル共重合体であって、例え
ばハイカーＣＴＢＮ１３００ｘ１３、同ＣＴ Ｂ Ｎ
１３００ｘ ９、同ＣＴＢＮ１３００ｘ ８、同ＣＴ
Ｂ Ｎ １３００Ｘ １５ （いずれもＢ、Ｆ、グツド
リッチケミカル社製）とし 憚て市販されている。こ
の（Ｂ）成分はエポキシ樹脂と反応して使用される。Component CB) is a liquid butadiene-acrylonitrile copolymer having carboxyl groups at both ends, such as Hiker CTBN 1300x13, Hiker CTBN
1300x 9, same CTBN1300x 8, same CT
It is commercially available as BN 1300X 15 (both B and F, manufactured by Gutdrich Chemical Co.). This component (B) is used by reacting with an epoxy resin.
（Ｂ）成分とエポキシ樹脂との反応は、カルボキシル基
１当量に対し、エポキシ樹脂２当囚以上使用して行う。The reaction between component (B) and the epoxy resin is carried out using two or more equivalents of epoxy resin per equivalent of carboxyl group.
エポキシ樹脂は通常共重合体に対し大過剰を使用しても
よく、このとき、未反応のエポキシ樹脂は（Ａ）成分の
エポキシ樹脂どして組成物中に存在する。ここで使用Ｊ
るエポキシ樹脂は、１種又は２ｗ！以上であってもよく
、特に好ましいエポキシ樹脂はグリシジルアミン系エポ
キシ樹脂である。The epoxy resin may usually be used in large excess with respect to the copolymer, and in this case, unreacted epoxy resin is present in the composition as the epoxy resin of component (A). used here J
The epoxy resin used is 1 type or 2w! The above may be used, and a particularly preferred epoxy resin is a glycidylamine-based epoxy resin.
この樹脂組成物に更にニトリルゴムを加える。それによ
って成形時の樹脂のフローを一層少くすることができる
。（Ｃ）成分の〜４５＊Ｍ％のものが使用される。また
、コモノマーとしてアクリル酸、メタクリル酸の少くと
も１つを２重量％以下含有するカルボキシル基変成ニト
リルゴムを使用することがＩ １８８向上の点から特に
好ましい。Nitrile rubber is further added to this resin composition. Thereby, the flow of resin during molding can be further reduced. ~45*M% of component (C) is used. Further, it is particularly preferable to use a carboxyl group-modified nitrile rubber containing 2% by weight or less of at least one of acrylic acid and methacrylic acid as a comonomer from the viewpoint of improving I188.
ニトリルゴムとしては例えばニラボール１゜４３．１０
４２．１０７２ （いずれも日本げＡ２社製）である。Examples of nitrile rubber include Nilaball 1°43.10
42.1072 (all manufactured by Nihonge A2).
（Ｄ）成分のアミノ置換ジフェニルスルホンは硬化剤で
あって、具体的には下式の４．４′−ジアミノジフェニ
ルスルホン（ＤＤＳ＞や
下記の３．３′、４．４′ −デトラアミノジフェニ
ルスルホン（ＴＤＳ）
を例示することができる。Ｄ、 Ｄ Ｓの単独使用又は
ＤＤＳとＴＤＳとの併用が好適である。The amino-substituted diphenyl sulfone of the component (D) is a curing agent, and specifically, 4,4'-diaminodiphenylsulfone (DDS> of the following formula) and 3.3',4,4'-detraamino An example is diphenylsulfone (TDS). It is preferable to use D, DS alone or in combination with DDS and TDS.
（Ｅ）成分はジシアンジアミド及びその硬化促進剤であ
る。この硬化促進剤としては、下式（ただしＸ、Ｙは同
−又は異なりでＨＸＣＲ，ＯＣＨ，を表わす。）
の尿素化合物が主に用いられる。このうち３（３，４−
ジクロルフェニル）−１，１−ジメチル尿素は、これを
用いるとボイドのない高強度の成形物が得られるので特
に好ましい。同硬化促進剤として他にイミダゾール化合
物特に２−フェニル−４−メチル−５−ヒドロキシメチ
ルイミダゾールや２−フェニル−４，５−ジヒドロキシ
メチルイミダゾールも使用できる。Component (E) is dicyandiamide and its curing accelerator. As this curing accelerator, a urea compound of the following formula (where X and Y are the same or different and represent HXCR, OCH) is mainly used. Of these, 3 (3,4-
Dichlorophenyl)-1,1-dimethylurea is particularly preferred since it provides void-free molded products with high strength. Other imidazole compounds, particularly 2-phenyl-4-methyl-5-hydroxymethylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole, can also be used as the curing accelerator.
本発明のエポキシ樹脂組成物は、硬化剤として（Ｄ）成
分と（Ｅ）成分とを°併せ含んでいるため、複合材料の
物性及び成形操作性を向上させることができる。すなわ
ち、成形操作性についていうと、硬化剤系がＣＤ）成分
単独の場合には一旦プレキコアーしたのち更に昇温し、
硬化反応を完了することが必要であるが、（Ｄ）物
成分と（Ｅ）成分を併用すると成形時の加熱を直接成
形湿度にまで高めることができ、このため成形操作を単
純化して生産性の向上を達成することができる。Since the epoxy resin composition of the present invention contains both components (D) and (E) as curing agents, it is possible to improve the physical properties and molding operability of the composite material. In other words, in terms of molding operability, when the curing agent system consists of the CD component alone, the temperature is further increased after pre-coring is performed.
Although it is necessary to complete the curing reaction, (D)
When component (E) is used in combination, the heating during molding can be directly increased to the molding humidity, thereby simplifying the molding operation and improving productivity.
び（Ｃ）成分の合計が３〜２５、好ましくは４〜２０重
量部、（Ｃ）／（Ｂ）： ０．２〜２．０好ましくは
０．５〜１．５、（Ｄ）成分１５〜５０好ましくは２０
〜４５重量部、〔Ｅ〕酸成分ジシアンジアミド及びその
硬化促進剤はそれぞれ０．２〜５．０好ま置部未満のと
きは硬化後の樹脂の伸度が低下し高伸度の複合材料が得
られず、また２５重量部を超えると複合材料の耐熱性が
低下する。（Ｄ）成分が１５重量部未満のときは複合材
料の耐熱性が低下し、また５０重量部を超えると複合材
料の耐水性が低下する。（Ｅ）成分のジシアンジアミド
及び硬化促進剤の夫々が０．２重量部未満のときはプレ
キュアを必要とするようになり、また５、０重量部を超
えると複合材料の耐熱性が低下する。and (C) component total is 3 to 25, preferably 4 to 20 parts by weight, (C)/(B): 0.2 to 2.0, preferably 0.5 to 1.5, (D) component 15 ~50 preferably 20
When the amount of [E] acid component dicyandiamide and its curing accelerator is less than 0.2 to 5.0 parts by weight, the elongation of the resin after curing decreases and a composite material with high elongation is obtained. If the amount exceeds 25 parts by weight, the heat resistance of the composite material will decrease. When component (D) is less than 15 parts by weight, the heat resistance of the composite material decreases, and when it exceeds 50 parts by weight, the water resistance of the composite material decreases. When each of component (E), dicyandiamide and curing accelerator, is less than 0.2 parts by weight, precure becomes necessary, and when it exceeds 5.0 parts by weight, the heat resistance of the composite material decreases.
本発明のエポキシ樹脂組成物は、強化材繊維に含浸し、
いわゆるプリプレグを経て複合材料に成形される。The epoxy resin composition of the present invention is impregnated into reinforcing fibers,
It is molded into a composite material through a so-called prepreg.
強化材繊維に本発明の樹脂組成物を含浸させプリプレグ
とするには該樹脂組成物をアセ１〜ン、メヂルエチルク
１ヘン、メチルレロソルブ等の溶剤に溶かし３０〜６０
重量％の′ａ度とし、これを強化材繊維に含浸させた後
、９０〜１２０℃で５〜１５分乾燥させ脱溶剤づる。In order to prepare a prepreg by impregnating reinforcing fibers with the resin composition of the present invention, the resin composition is dissolved in a solvent such as acetone, methyl ethyl alcohol, or methyl rerosolve at a concentration of 30 to 60%.
The reinforcing material fibers are impregnated with this, and then dried at 90 to 120°C for 5 to 15 minutes to remove the solvent.
プリプレグの樹脂含有率は３０−５０重量％が一般的で
ある。本発明の樹脂組成物をマトリックスとしたプリプ
レグの成形はプレキュアすることなく直接１６０〜１９
０℃に昇温し、５０〜２５０分間維持することにより行
うことができ、作業効率が高い。The resin content of prepreg is generally 30-50% by weight. The prepreg using the resin composition of the present invention as a matrix can be molded directly without pre-curing.
This can be done by raising the temperature to 0°C and maintaining it for 50 to 250 minutes, and the work efficiency is high.
本発明の樹脂組成物をマトリックスとし伸度１．８％、
引張強１衰４４１ｋｏ ／ｎ＋ｍ’ 、引張弾性率２４
．５Ｔｏｎ／ｍｍ２の炭素繊維を強化材繊維どした一方
向性炭素ｌＩＡ維複合材料の物性は次の通りである。The resin composition of the present invention is used as a matrix, and the elongation is 1.8%.
Tensile strength 1 decay 441ko/n+m', tensile modulus 24
．． The physical properties of a unidirectional carbon IIA fiber composite material in which 5 Ton/mm2 of carbon fiber is used as a reinforcing material are as follows.
引張 強度 ２００ｋ（］ ／ｍｍ２以上引張弾性
率 １３．５〜１５．５丁ｏｎ／ ｍｍ’引張破断
伸度 １．５％以上
ＩＬＳＳ （室温） １１．０〜１３．５ｋｇ／
ｍｍ’ＩＬＳＳ （１００℃） ７−９．５ｋＯ／
１１１ｍ’本発明のエポキシ樹脂組成物は、前記した
高伸度炭素１ｖ４帷を強化材繊維とづるほか、ガラス繊
維、芳香族ポリアミド繊肩（ｔｒどを単独又は（）１用
して強化材繊維とする複合材料のマトリックス樹脂どし
て有効に使用することができる。Tensile strength 200k(]/mm2 or more Tensile modulus 13.5-15.5 on/mm'Tensile elongation at break 1.5% or more ILSS (room temperature) 11.0-13.5kg/
mm'ILSS (100℃) 7-9.5kO/
111m' The epoxy resin composition of the present invention uses the above-mentioned high elongation carbon 1v4 strip as a reinforcing fiber, and also uses glass fiber, aromatic polyamide fiber shoulder (TR, etc.) alone or as a reinforcing fiber. It can be effectively used as a matrix resin for composite materials.
以下、本発明の実施例を比較例と共に示す。Examples of the present invention will be shown below along with comparative examples.
実施例１
アラルダイトＭ Ｙ −７２０（ヂバ・カイギー社製）
８０重量部、ダウエポキシＸ Ｄ −７８５５（ダウケ
ミカル社製）２０重量部、ハイカーＣＴ Ｂ Ｎ １３
００ｘ１３（Ｂ、Ｆ、グツドリッチケミカル社製）５重
量部どアラルダイトＭ Ｙ −７２０（チバ・ガイギー
シ社＠１）１０重１部との反応物、二ｉ−リルゴム、ニ
ラポール１０７２ （日本ゼオン社製） ３ｐ、４．４
＝ニジアノシフ１ニルスルホン３重開部、ジシアンジア
ミド０．８重量部、３（３，４−ジクロロフェニル）−
１，１−ジメチル尿素１．０重量部をメチルエチルケト
ン−メチルセロソルブ混合溶剤に溶かし３５％溶液とし
た。Example 1 Araldite MY-720 (manufactured by Jiba Kaigy)
80 parts by weight, 20 parts by weight of Dowepoxy X D-7855 (manufactured by Dow Chemical Company), Hiker CT B N 13
00x13 (B, F, manufactured by Gutdrich Chemical Co., Ltd.) 5 parts by weight Araldite M Y-720 (Ciba-Geigyshi Co., Ltd. @1) Reaction product with 10 parts by weight, Ni-Ryl rubber, Nirapol 1072 (Nippon Zeon Co., Ltd.) (manufactured by) 3p, 4.4
= Nidianosif 1 Nyl sulfone triple opening, 0.8 parts by weight of dicyandiamide, 3(3,4-dichlorophenyl)-
1.0 parts by weight of 1,1-dimethylurea was dissolved in a mixed solvent of methyl ethyl ketone and methyl cellosolve to form a 35% solution.
この樹脂溶液を伸度１．８５％の炭素繊維へスフ７・イ
１−■Ｓ丁−６０００（東邦ベスロン社製）に含浸させ
たのち乾燥した。Carbon fibers having an elongation of 1.85% were impregnated with this resin solution into carbon fibers having an elongation of 1.85% and then dried.
この場合の樹脂含有量は４０重置火であり、一方向のプ
リプレグを得た。このプリプレグのコンポジット物性を
測定した。In this case, the resin content was 40 times, and a unidirectional prepreg was obtained. The composite physical properties of this prepreg were measured.
引張 強度 ２２７ｋＵ ／ｍｍ２以上引張弾性
率 １３．８ ”’ｊ ｏｎ／ ｍｍ’引張破断
伸度 １．６５％
ＩＬＳＳＣ室’ｔＡ）１２．３ｋｇ／ｍｍ’ｆ Ｌ Ｓ
Ｓ （，１００℃） ８．０ｋｇ／ｍｍ２実施
例２〜９
エポキシ樹脂組成物の組成を変え実施例１と同様の方法
にて成形物を得た。その結果を第１表に示寸。Tensile strength 227kU/mm2 or more Tensile modulus 13.8 ”'j on/mm' Tensile elongation at break 1.65% ILSSC chamber'tA) 12.3kg/mm'f L S
S (, 100°C) 8.0 kg/mm2 Examples 2 to 9 Molded products were obtained in the same manner as in Example 1 except that the composition of the epoxy resin composition was changed. The results are shown in Table 1.
比較例１゜
現在航空機用に実用化されている１８０℃硬化型の炭素
繊維プリプレグ用耐熱性エポキシ樹脂と■
引張破断伸度１．８５％の炭素ｍ帷ベスファイトＳ Ｔ
−６０００（東邦ベスロン社製）を用いて一方面プリ
プレグを作った。このプリプレグの一方面コンポジット
特性は次の如くであった。Comparative Example 1 Heat-resistant epoxy resin for carbon fiber prepreg, cured at 180°C, which is currently in practical use for aircraft, and carbon fiber Besphite S T with tensile elongation at break of 1.85%.
A one-sided prepreg was made using -6000 (manufactured by Toho Bethlon). The one-sided composite properties of this prepreg were as follows.
引張 強度 ２１２ｋｇ ／ｎ＋ｎ＋２引張弾
性率 １５．７Ｔ ｏｎ／ ｍｍ’引張破断伸
度 １．３５％
ＩＬＳＳ（室温） １３．１ｋｇ／ ｎ＋ｎ＋’Ｉ
ＬＳＳ（１００℃） １０．０ｋｇ／ｍｍ２１００℃
でのＩ ＬＳＳ値は高く耐熱性は優れているが引張破断
伸度が低い。Tensile strength 212kg/n+n+2 Tensile modulus 15.7T on/mm' Tensile elongation at break 1.35% ILSS (room temperature) 13.1kg/n+n+'I
LSS (100℃) 10.0kg/mm2100℃
The ILSS value is high and the heat resistance is excellent, but the tensile elongation at break is low.
比較例２゜
現在航空機用に実用化されている１２０℃硬化型の炭素
繊維プリプレグ用エポキシ樹脂を用いて比較例１と全く
同様にして一方面炭素Ｉ１組プリプレグを作成し、その
コンポジット特性を測定した。Comparative Example 2 Using a 120°C curing type carbon fiber prepreg epoxy resin that is currently in practical use for aircraft, one-sided carbon I set prepreg was created in exactly the same manner as in Comparative Example 1, and its composite properties were measured. did.
引張 強度 ２２５ｋｇ／ｍｍ’引張弾性率
１４．ＯＴ ｏｎ／ ｍｍ’引張破断伸度
１．６１％
Ｉ ＬＳＳ ＜室ｆｍ ＞ ９．７ｋＱ／ ｍｌ
’ＩＬＳＳ（１００℃） ４．３ｋｇ／ｍｍ２引張
破断伸度は高いが１００℃でのＩＬＳＳ値が低く耐熱性
が劣る。Tensile strength 225kg/mm'Tensile modulus
14. OT on/mm' tensile elongation at break
1.61% I LSS <Chamber fm> 9.7kQ/ml
'ILSS (100°C) 4.3kg/mm2 Although the tensile elongation at break is high, the ILSS value at 100°C is low and the heat resistance is poor.
特許出願人 東邦ヘスロン林式会社 代理人弁理士 土 居 三 部 １８１ ンPatent applicant: Toho Hesron Hayashiki Company Representative Patent Attorney, Third Department 181 hmm
Claims (3)
ンーアクリロニ１〜リル共重合体 （Ｃ）ニトリルゴム （Ｄ）アミン置換ジフェニルスルホン （Ｅ）ジシアンジアミド及びその硬化促進剤 とを含み且つ、（Ｂ）成分をエポキシ 樹脂との反応物として含むエポキシ樹 脂組成物。(1) The following components (A), (B), (C), (D) (E) (A) Epoxy resin (B) Liquid butadiene-acryloni-1-lyl copolymer with carboxyl groups at both ends An epoxy resin composition comprising (C) nitrile rubber (D) amine-substituted diphenyl sulfone (E) dicyandiamide and its curing accelerator, and (B) component as a reaction product with an epoxy resin.
（Ｃ）成分の合計３〜２５重量部、（Ｄ）成分１５〜５
０重聞部、（Ｅ）成分のジシアンジアミド及びその硬化
促進剤それぞれ０．２〜５．０重量部を含む特許請求の
範囲（１）のエポキシ樹脂組成物。(2) A total of 3 to 25 parts by weight of component B) and component (C) per 100 parts by weight of component (A), and 15 to 5 parts by weight of component (D).
The epoxy resin composition according to claim (1), which contains 0 parts by weight, dicyandiamide as component (E), and 0.2 to 5.0 parts by weight of its curing accelerator.
３０重量％以上含む特許請求の範囲（１）のエポキシ樹
脂組成物。(3) The epoxy resin composition according to claim (1), in which component (A) contains 30% by weight or more of a glycidylamine-based epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8331583A JPS59207919A (en) | 1983-05-12 | 1983-05-12 | Epoxy resin composition of high elongation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8331583A JPS59207919A (en) | 1983-05-12 | 1983-05-12 | Epoxy resin composition of high elongation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59207919A true JPS59207919A (en) | 1984-11-26 |
| JPS6338049B2 JPS6338049B2 (en) | 1988-07-28 |
Family
ID=13798986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8331583A Granted JPS59207919A (en) | 1983-05-12 | 1983-05-12 | Epoxy resin composition of high elongation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59207919A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02219853A (en) * | 1989-02-21 | 1990-09-03 | Matsushita Electric Works Ltd | Resin composition for wiring board and prepreg |
| US6242083B1 (en) | 1994-06-07 | 2001-06-05 | Cytec Industries Inc. | Curable compositions |
| JP2001348418A (en) * | 2000-06-06 | 2001-12-18 | Mitsui Chemicals Inc | Epoxy resin composition and adhesive sheet |
| WO2004048435A1 (en) * | 2002-11-28 | 2004-06-10 | Mitsubishi Rayon Co., Ltd. | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these |
| JP2005281488A (en) * | 2004-03-30 | 2005-10-13 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated plate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0260845A (en) * | 1988-08-29 | 1990-03-01 | Oi Seisakusho Co Ltd | Device for sliding powdered seat |
-
1983
- 1983-05-12 JP JP8331583A patent/JPS59207919A/en active Granted
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02219853A (en) * | 1989-02-21 | 1990-09-03 | Matsushita Electric Works Ltd | Resin composition for wiring board and prepreg |
| US6242083B1 (en) | 1994-06-07 | 2001-06-05 | Cytec Industries Inc. | Curable compositions |
| JP2001348418A (en) * | 2000-06-06 | 2001-12-18 | Mitsui Chemicals Inc | Epoxy resin composition and adhesive sheet |
| WO2004048435A1 (en) * | 2002-11-28 | 2004-06-10 | Mitsubishi Rayon Co., Ltd. | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these |
| JPWO2004048435A1 (en) * | 2002-11-28 | 2006-03-23 | 三菱レイヨン株式会社 | Epoxy resin for prepreg, prepreg, fiber reinforced composite material, and production method thereof |
| US7591973B2 (en) | 2002-11-28 | 2009-09-22 | Mitsubishi Rayon Co., Ltd. | Method for producing a fiber-reinforced composite material plate |
| JP4603978B2 (en) * | 2002-11-28 | 2010-12-22 | 三菱レイヨン株式会社 | Manufacturing method of fiber reinforced composite material molded article |
| US7959838B2 (en) | 2002-11-28 | 2011-06-14 | Mitsubishi Rayon Co., Ltd. | Epoxy resin for prepreg, prepreg, fiber-reinforced composite material and methods for production thereof |
| US8470435B2 (en) | 2002-11-28 | 2013-06-25 | Mitsubishi Rayon Co., Ltd. | Epdxy resin for prepreg, prepreg, fiber-reinforced composite material, and methods for production thereof |
| US8486518B2 (en) | 2002-11-28 | 2013-07-16 | Mitsubishi Rayon Co., Ltd. | Epoxy resin for prepreg, prepreg, and fiber-reinforced composite material and methods for production thereof |
| JP2005281488A (en) * | 2004-03-30 | 2005-10-13 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6338049B2 (en) | 1988-07-28 |
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