JPH03243619A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH03243619A JPH03243619A JP4051490A JP4051490A JPH03243619A JP H03243619 A JPH03243619 A JP H03243619A JP 4051490 A JP4051490 A JP 4051490A JP 4051490 A JP4051490 A JP 4051490A JP H03243619 A JPH03243619 A JP H03243619A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- pts
- manufactured
- weight
- curing
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 16
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 9
- 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 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- WLXDNZNRANJXCS-UHFFFAOYSA-N [B].[F].[F].[F] Chemical compound [B].[F].[F].[F] WLXDNZNRANJXCS-UHFFFAOYSA-N 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 229920003319 Araldite® Polymers 0.000 description 6
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 5
- 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
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- -1 boron trifluoride compound Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 230000000704 physical effect Effects 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
- 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 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はエポキシ樹脂組成物に関し、特に高性能構造材
料用マトリックス樹脂として有用な、保存安定性に優れ
たプリプレグ用のエポキシ樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition, and particularly to an epoxy resin composition for prepregs that has excellent storage stability and is useful as a matrix resin for high-performance structural materials.
エポキシ樹脂は、耐熱性、弾性率、硬度及び耐薬品性に
優れており、特に炭素繊維、ガラス繊維、アラミド繊維
等の強化繊維とマトリックス樹脂からなる複合材料用の
マトリックス樹脂として、広く使用されている。ただ、
大きな強度や耐熱性、耐水性等を必要とする用途、例え
ば航空機等の構造材料としての用途などには、自ずと使
用し得るエポキシ樹脂や硬化剤は限定されてしまう。Epoxy resin has excellent heat resistance, elastic modulus, hardness, and chemical resistance, and is widely used as a matrix resin for composite materials made of matrix resin and reinforcing fibers such as carbon fiber, glass fiber, and aramid fiber. There is. just,
Epoxy resins and curing agents that can be used are naturally limited to applications that require high strength, heat resistance, water resistance, etc., such as applications as structural materials for aircraft and the like.
近年、航空機用その他の高性能構造材料用エポキシ樹脂
の硬化剤として、ジアミノジフェニルスルホン（以下Ｄ
Ｏ５と略記する）がしばしば用いられている。特に、Ｎ
、Ｎ、Ｎ’ 、Ｎ’−テトラグリシジルジアミノジフェ
ニルメタン等の耐熱性グリシジルアミン型エポキシ樹脂
の場合、硬化剤として００５を用いると、熱変形温度の
高い硬化物が得られ、しかもその樹脂組成物は比較的長
いポットライフを有するため、プリプレグ用樹脂組成物
として使用することができる。In recent years, diaminodiphenylsulfone (D) has been used as a curing agent for epoxy resins for aircraft and other high-performance structural materials.
(abbreviated as O5) is often used. In particular, N
In the case of heat-resistant glycidylamine type epoxy resins such as , N, N', N'-tetraglycidyldiaminodiphenylmethane, when 005 is used as a curing agent, a cured product with a high heat distortion temperature can be obtained, and the resin composition has Since it has a relatively long pot life, it can be used as a resin composition for prepreg.
ところが、ＤＯ５はそれ単独では硬化特性が良好でなく
、硬化不良を避けるためには、より長時間。However, DO5 alone does not have good curing characteristics, and in order to avoid poor curing, it must be cured for a longer time.
高温で成形する必要があるという欠点を有している。そ
こで硬化特性を改善するために、ＤＯ５とジシアンジア
ミド（以下ＤＩＣＹと略記する）とを併用することか提
案されている（特開昭５１−１５１７６７号、特開昭５
８−８３０３１号、特開昭５９−２０７９１９号、特開
昭５９２０７９２０号公報）。ただ、ＤＤＳ−ＤＩＣＹ
系においても。It has the disadvantage of requiring molding at high temperatures. Therefore, in order to improve the curing properties, it has been proposed to use DO5 and dicyandiamide (hereinafter abbreviated as DICY) in combination (JP-A-51-151767;
8-83031, JP-A-59-207919, JP-A-59207920). However, DDS-DICY
Also in the system.
充分な硬化特性を得る場合には、プリプレグとしての保
存安定性が不良になるという問題がある。When obtaining sufficient curing properties, there is a problem that storage stability as a prepreg becomes poor.
従って、本発明の目的は、複合材料としたときの硬化特
性が良好であって、しかもプリプレグとしたときのタッ
ク性、保存安定性にも優れたエポキシ樹脂組成物を提供
することにある。Therefore, an object of the present invention is to provide an epoxy resin composition that has good curing properties when made into a composite material and also has excellent tackiness and storage stability when made into a prepreg.
本発明者らは、鋭意研究を重ねた結果、エポキシ樹脂用
硬化剤として、ＤＯ５／ＤＩＣＹ系において、硬化促進
剤として三弗化ホウ素化合物を特定量配合した系が、上
記目的に適合することを知見し、本発明を完成するに至
った。As a result of extensive research, the present inventors have found that a system containing a specific amount of a boron trifluoride compound as a curing accelerator in the DO5/DICY system as a curing agent for epoxy resins is suitable for the above purpose. These findings led to the completion of the present invention.
すなわち、本発明によれば、エポキシ樹脂１００重量部
に対し、ジアミノジフェニルスルホン２８〜５０重量部
、ジシアンジアミド２．０〜５．０重量部及び三弗化ホ
ウ素硬化促進剤０．１〜０．３重量部を配合したことを
特徴とするエポキシ樹脂組成物が提供される。That is, according to the present invention, 28 to 50 parts by weight of diaminodiphenylsulfone, 2.0 to 5.0 parts by weight of dicyandiamide, and 0.1 to 0.3 parts by weight of the boron trifluoride curing accelerator are added to 100 parts by weight of the epoxy resin. There is provided an epoxy resin composition characterized in that it contains parts by weight.
本発明のエポキシ樹脂組成物を用いることにより、プリ
プレグとしてのタック性、保存安定性に優れ、しかも複
合材料としたとき硬化特性の良好な成形体を得ることが
できる。By using the epoxy resin composition of the present invention, it is possible to obtain a molded article that has excellent tackiness and storage stability as a prepreg, and also has good curing characteristics when used as a composite material.
本発明で用いるエポキシ樹脂は、特に制限されるもので
はなく、ビスフェノールＡ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、ウレタン変性ビスフェノールＡ型エポキ
シ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂等であ
る。The epoxy resin used in the present invention is not particularly limited, and includes bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, glycidylamine epoxy resin, alicyclic epoxy resin, urethane-modified bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, etc.
これらのエポキシ樹脂は混合して用いるのが好ましい。It is preferable to use a mixture of these epoxy resins.
耐熱性が要求される場合には、グリシジルアミン型エポ
キシ樹脂を用いるのが好ましく、特にグリシジルアミン
型エポキシ樹脂が全エポキシ樹脂中の３０重量％以上の
場合に耐熱性が良好なものとなる。When heat resistance is required, it is preferable to use a glycidylamine type epoxy resin. In particular, when the glycidylamine type epoxy resin accounts for 30% by weight or more of the total epoxy resin, the heat resistance becomes good.
グリシジルアミン型エポキシ樹脂の具体例としては、Ｎ
、Ｎ、Ｎ’ 、Ｎ’−テトラグリシジルジアミノジフェ
ニルメタン〔アラルダイトＭＹ７２０（チバ・ガイギー
社製）、ＥＬＭ４３４（住人化学工業社製）、エボトー
トＹＨ４３４（東部化成社製）、ＥＰ６０４（油化シェ
ルエポキシ社製）〕、テトラグリシジルメタキシレンジ
アミン、Ｎ、Ｎ、Ｏ−トリグリシジルメタアミノフェノ
ール（ＥＬＭ１２０（住人化学工業社製）、エボトート
ＹＤＭ１２０（東部化成社製））、 Ｎ、Ｎ、Ｏ−トリ
グリシジルバラアミノフｍ ／ −ル［ＥＬＭｌｏｏ（
住人化学工業社製）、ＹＸ−４（油化シェルエポキシ社
ｍ１））などが挙げられる。Specific examples of glycidylamine type epoxy resin include N
, N, N', N'-tetraglycidyldiaminodiphenylmethane [Araldite MY720 (manufactured by Ciba Geigy), ELM434 (manufactured by Sumima Kagaku Kogyo Co., Ltd.), Evoto YH434 (manufactured by Tobu Kasei Co., Ltd.), EP604 (manufactured by Yuka Shell Epoxy Co., Ltd.) )], tetraglycidyl metaxylene diamine, N, N, O-triglycidyl meta-aminophenol (ELM120 (manufactured by Sumima Kagaku Kogyo Co., Ltd.), Evoto YDM120 (manufactured by Tobu Kasei Co., Ltd.)), N, N, O-triglycidyl baramino Hm/-le [ELMloo(
YX-4 (manufactured by Yuka Shell Epoxy Co., Ltd.)) and YX-4 (manufactured by Yuka Shell Epoxy Co., Ltd.).
フェノールノボラック型エポキシ樹脂は、例えばエピコ
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、ＥＰＮ１１３９（
チバ・ガイギー社製）、ダウエポキシＤＥＮ４３１．
ＤＥＮ４３８、ＤＥ〜４３９、ＸＤ７８５５ （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）などの
商品名で市販されている。また。Phenol novolac type epoxy resins include, for example, Epicote 152, Epicote 154 (manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite EPN1138, EPN1139 (
Ciba Geigy), Dowepoxy DEN431.
It is commercially available under trade names such as DEN438, DE~439, XD7855 (manufactured by Dow Chemical Co.), EPPN201 (manufactured by Nippon Kayaku Co., Ltd.), and Epiclon N740 (manufactured by Dainippon Ink and Chemicals Co., Ltd.). Also.
クレゾールノボラック型エポキシ樹脂は、チバ・ガイギ
ーＥＣＮ１２３５． ＥＣＮ１２７３、ＥＣＮ１２８０
、ＥＣＮ１２９９（チバ・ガイギー社製）、ＥＣＮ１２
７０４（日本化薬社製）、ＥＳＣＮ４２０（住人化学工
業社製）などの商品名で市販されている。The cresol novolak type epoxy resin is Ciba Geigy ECN1235. ECN1273, ECN1280
, ECN1299 (manufactured by Ciba Geigy), ECN12
It is commercially available under trade names such as 704 (manufactured by Nippon Kayaku Co., Ltd.) and ESCN420 (manufactured by Sumima Kagaku Kogyo Co., Ltd.).
ビスフェノールＡ型エポキシ樹脂としては公知のものを
用いることができ、市販品として例えば。As the bisphenol A type epoxy resin, known ones can be used, such as commercially available products.
エピコート８２８、エピコート８３４、エピコート８２
７、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１００
９（油化シェルエポキシ社製）、アラルダイトＣＹ２Ｏ
５、（１，Ｙ２３０− ＣＹ２３２、ＣＹ２２１． Ｇ
Ｙ２５７、ＧＹ２５２、ＧＹ２５５、ＧＹ２５０、ＧＹ
２６０、ＧＹ２８０、アラルダイト６０７１、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，ＤＥＲ３３２，Ｄ
ＥＲ６６２、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、
ＹＤ１１５−ＣＡ、ＹＤ−１１７、ＶＤ−１２１、ＹＤ
−１２７、ＹＤ−１２８、ＶＤ−１２８ＣＡ、 ＶＤ−
１２８５，ＹＳ−１３４，ＹＤ−００１２，ＹＤ−０１
１、ＶＤ−０１２、ＹＤ−０１４、ＹＤ−０１４ＥＳ、
ＹＤ−０１７、ＹＤ−０１９、ＹＤ−０２０，ＹＤ−０
０２（東部化成社製）などが挙げられる。Epicote 828, Epicote 834, Epicote 82
7. Epicote 1001, Epicote 1002, Epicote 1004, Epicote 1007, Epicote 100
9 (manufactured by Yuka Shell Epoxy Co., Ltd.), Araldite CY2O
5, (1, Y230- CY232, CY221.G
Y257, GY252, GY255, GY250, GY
260, GY280, Araldite 6071, Araldite 7071, Araldite 7072 (manufactured by Ciba Geigy), Dowepoxy DER331, DER332, D
ER662, DER663U, DER662U (manufactured by Dow Chemical Company), Epicron 840.850.855.
860.1050.3050.4050.7050 (manufactured by Dainippon Ink Chemical Industries, Ltd.), Epotote YD-115,
YD115-CA, YD-117, VD-121, YD
-127, YD-128, VD-128CA, VD-
1285, YS-134, YD-0012, YD-01
1, VD-012, YD-014, YD-014ES,
YD-017, YD-019, YD-020, YD-0
02 (manufactured by Tobu Kasei Co., Ltd.).
脂環式エポキシ樹脂としては、市販品として例えば、ア
ラルダイトＣＹ−１７９、ＣＹ−１７８、ＣＹ−１８２
、ＣＹ１８３（チバガイギー社製）などが挙げられる。Examples of commercially available alicyclic epoxy resins include Araldite CY-179, CY-178, and CY-182.
, CY183 (manufactured by Ciba Geigy).
ウレタン変性ビスフェノールＡ型エポキシ樹脂としては
、例えばアデカレジンＥＰＶ−６、ＥＰＶ−１０、ＥＰ
Ｖ−１５（旭電化社製）が挙げられる。また、臭素化ビ
スフェノールＡ型エポキシ樹脂としては、エピクロン１
５２、１１２０（大日本インキ化学工業社製）、ＥＳＢ
３４０（住人化学工業社製）、エピコート１０５０（油
化シェルエポキシ社製）などが挙げられる。Examples of urethane-modified bisphenol A epoxy resins include Adekal resin EPV-6, EPV-10, and EP
V-15 (manufactured by Asahi Denka Co., Ltd.) is mentioned. In addition, as a brominated bisphenol A epoxy resin, Epiclon 1
52, 1120 (manufactured by Dainippon Ink and Chemicals), ESB
340 (manufactured by Susumu Kagaku Kogyo Co., Ltd.) and Epicoat 1050 (manufactured by Yuka Shell Epoxy Co., Ltd.).
ＤＤＳには、４．４’−５３，３’−１３，４′−等の
異性体やそれらの混合物があるが、本発明においてはこ
れらの何れも使用することができる。４．４’−ＤＤＳ
は他の異性体に比へ耐熱性は高いが吸水率が大きし１と
か、３ 、３’−ＤＤＳは弾性率は高いがガラス転移温
度が低し）とかいう特徴があるので、目的とする複合材
料の重視される物性に応じて、適宜選択使用することが
できる。DDS includes isomers such as 4,4'-53, 3'-13,4' and mixtures thereof, and any of these can be used in the present invention. 4.4'-DDS
Compared to other isomers, 3,3'-DDS has high heat resistance but high water absorption (1), and 3,3'-DDS has high elastic modulus but low glass transition temperature. They can be appropriately selected and used depending on the important physical properties of the material.
また、三弗化ホウ素硬化促進剤としては、三弗化ホウ素
アミン錯体、特にモノエチルアミン錯体（以下Ｅ ｔ
Ｎ ｌ（、錯体と略記する）が好んで用し）られる。In addition, as a boron trifluoride curing accelerator, a boron trifluoride amine complex, particularly a monoethylamine complex (hereinafter referred to as E t
Nl (abbreviated as complex) is preferably used.
本発明においては、前記硬化剤系はエポキシ樹脂１００
重量部に対し、ＤＤ５２８〜５０重量部（好ましくは３
０〜４５重量部）、ＤＩＣＹ２．０−５．０重量部（好
ましくは２゜５〜４．５重量部）、三弗化ホウ素硬化促
進剤０．１〜０．３重量部（好ましくは０．１−０．２
重量部）配合される。ＤＤＳが２８重量部未満では、成
形時の樹脂フローが過多となり、且つ成形物の表面性が
不良となる。また、硬化不良となり硬化物の諸物性、特
に耐熱性が低下する。逆に５０重量部を超過すると、混
合溶解に長時間を要すると共に、保存安定性も不良とな
る。また、ＤＩＣＹが２゜０重量部未満あるいは三弗化
ホウ素硬化促進剤が０．１重量部未満では、硬化特性が
不良となり、硬化に長時間を要すると共に硬化物の諸物
性、特に機械的特性が低下する。逆に、ＤＩＣＹが５．
０重量部超過あるいは三弗化ホウ素硬化促進剤が０．３
重量部超過では、保存安定性が不良となる。In the present invention, the curing agent system is an epoxy resin 100%
DD528 to 50 parts by weight (preferably 3 parts by weight)
0 to 45 parts by weight), DICY 2.0 to 5.0 parts by weight (preferably 2.5 to 4.5 parts by weight), boron trifluoride curing accelerator 0.1 to 0.3 parts by weight (preferably 0 .1-0.2
parts by weight). If DDS is less than 28 parts by weight, resin flow during molding will be excessive and the surface properties of the molded product will be poor. Moreover, curing becomes insufficient, and various physical properties of the cured product, especially heat resistance, deteriorate. On the other hand, if it exceeds 50 parts by weight, it will take a long time to mix and dissolve and the storage stability will be poor. Furthermore, if the DICY is less than 2.0 parts by weight or the boron trifluoride curing accelerator is less than 0.1 parts by weight, the curing properties will be poor, it will take a long time to cure, and the physical properties of the cured product, especially the mechanical properties, will be poor. decreases. On the other hand, DICY is 5.
Exceeding 0 parts by weight or boron trifluoride curing accelerator 0.3
If the amount exceeds the weight part, the storage stability will be poor.
本発明のエポキシ樹脂組成物には、靭性向上のためにポ
リエーテルスルホン等の熱可塑性樹脂を配合することが
できるし、また充填剤、希釈剤等の添加剤を配合するこ
ともできる。The epoxy resin composition of the present invention may contain a thermoplastic resin such as polyether sulfone to improve toughness, and may also contain additives such as fillers and diluents.
なお、本発明のエポキシ樹脂組成物は、複合材料とした
ときに優れた硬化特性、機械的物性を有するので、高性
能複合材料用マトリックス樹脂として使用され、航空、
宇宙、車両、船舶等の構造材料用として利用される。も
ちろん、本発明のエポキシ樹脂組成物は、土木建築用材
料、塗料、ランニング材、接着剤、電気機器成形材料（
機械部品、治工具）等としても使用することができる。The epoxy resin composition of the present invention has excellent curing properties and mechanical properties when made into a composite material, so it is used as a matrix resin for high-performance composite materials, and is used in aviation,
Used as a structural material for space, vehicles, ships, etc. Of course, the epoxy resin composition of the present invention can be used in civil engineering and construction materials, paints, running materials, adhesives, electrical equipment molding materials (
It can also be used as machine parts, jigs, tools, etc.
本発明のエポキシ樹脂組成物は、前記構成としたことか
ら、次のような卓越した効果を奏する。Since the epoxy resin composition of the present invention has the above structure, it exhibits the following outstanding effects.
（イ）プリプレグとしたときの保存安定性が良好である
。(a) Good storage stability when made into prepreg.
（ロ）硬化特性が良好で、硬化成形時に樹脂が流れ過ぎ
ないし、しかも完全に硬化する。(b) Good curing properties, the resin does not flow too much during curing and molding, and is completely cured.
（ハ）機械的物性、耐熱性の良好な成形体が得られる。(c) A molded article with good mechanical properties and heat resistance can be obtained.
次に、実施例及び比較例により本発明を更に詳細に説明
する。Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例１〜３
本実施例では、グリシジルアミン型４官能エポキシ樹脂
として二ピコ−トロ０４（油化シェルエポキシ社製）を
、ビスフェノールＡ型エポキシ樹脂としてエピコート１
００４（油化シェルエポキシ社製）を、硬化剤としては
４．４’−ＤＤＳ／ＤＩＣＹ／ＢＦ、・ＥｔＮＨ２錯体
系を使用し、プリプレグ用のマトリックス樹脂を調製し
た。Examples 1 to 3 In this example, Nipico-Toro 04 (manufactured by Yuka Shell Epoxy Co., Ltd.) was used as a glycidylamine type tetrafunctional epoxy resin, and Epicoat 1 was used as a bisphenol A type epoxy resin.
A matrix resin for prepreg was prepared using 004 (manufactured by Yuka Shell Epoxy Co., Ltd.) and 4.4'-DDS/DICY/BF, .EtNH2 complex system as a curing agent.
各実施例において、先ずエピコート６０４／エピコート
１００４＝７／３（重量比）の割合で、両者を１２０℃
で加熱混合する。次に、該混合物に４．４’−００５を
表−１に示す割合で添加し、混合撹拌して溶解させる。In each example, first, both were heated to 120° C. at a ratio of 7/3 (weight ratio) of Epicoat 604/Epicoat 1004.
Heat and mix. Next, 4.4'-005 was added to the mixture in the proportions shown in Table 1, and the mixture was mixed and stirred to dissolve.
その後８０℃まで冷却し、更にこれにＤＩＣＹとＢＦ、
・ＥｔＮＨ，錯体を表−１に示す割合で添加し、数分間
撹拌してエポキシ樹脂組成物を調製した。After that, it was cooled to 80℃, and further DICY and BF were added to it.
- EtNH and the complex were added in the proportions shown in Table 1, and stirred for several minutes to prepare an epoxy resin composition.
上記で得たエポキシ樹脂を一方向に揃えた炭素繊維（強
度３５０ｋｇ／ａ＋ｍ 、弾性率３２ｔ／ａｍ”）に含
浸させ、プリプレグを得た。このプリプレグのタック値
をタック測定機（東洋精機■製ピクマタツク）を用し）
て測定した。その結果を表−１に示す。The epoxy resin obtained above was impregnated into carbon fibers aligned in one direction (strength 350 kg/a+m, elastic modulus 32 t/am") to obtain a prepreg. The tack value of this prepreg was measured using a tack measuring device (manufactured by Toyo Seiki ■). (Using Pikuma Tatsu)
It was measured using The results are shown in Table-1.
これらのプリプレグは製造時の作業性もよく、且つタッ
ク性、保存安定性、樹脂フロー性、硬化度等のプリプレ
グとしての特性も良好であり、また硬化物のＴｇも良好
であった。These prepregs had good workability during production, and also had good properties as a prepreg such as tackiness, storage stability, resin flowability, and degree of curing, and the Tg of the cured product was also good.
比較例１〜８
実施例と同一の配合比のエポキシ樹脂に表−１に示す配
合比で硬化剤系を添加し、実施例と同様にしてエポキシ
樹脂組成物及びプリプレグを作製し試験を行なった。そ
の結果を表−１に示す。Comparative Examples 1 to 8 A curing agent system was added to the epoxy resin at the same blending ratio as in the example, and a curing agent system was added at the blending ratio shown in Table 1, and epoxy resin compositions and prepregs were prepared and tested in the same manner as in the example. . The results are shown in Table-1.
表−１からこの比較例のプリプレグは本発明品に比較し
て、諸性状が悪いことが分る。From Table 1, it can be seen that the prepreg of this comparative example has poorer properties than the product of the present invention.
Claims (1)
ェニルスルホン２８〜５０重量部、ジシアンジアミド２
．０〜５．０重量部及び三弗化ホウ素硬化促進剤０．１
〜０．３重量部を配合したことを特徴とするエポキシ樹
脂組成物。(1) For 100 parts by weight of epoxy resin, 28 to 50 parts by weight of diaminodiphenylsulfone, 2 parts by weight of dicyandiamide
．． 0 to 5.0 parts by weight and 0.1 part by weight of boron trifluoride curing accelerator
An epoxy resin composition characterized in that it contains ~0.3 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4051490A JPH03243619A (en) | 1990-02-20 | 1990-02-20 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4051490A JPH03243619A (en) | 1990-02-20 | 1990-02-20 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03243619A true JPH03243619A (en) | 1991-10-30 |
Family
ID=12582642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4051490A Pending JPH03243619A (en) | 1990-02-20 | 1990-02-20 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03243619A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620510B1 (en) | 1998-12-25 | 2003-09-16 | Mitsubishi Rayon Co., Ltd. | Epoxy resin composition, prepreg, and roll made of resin reinforced with reinforcing fibers |
| JP2005281488A (en) * | 2004-03-30 | 2005-10-13 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated plate |
| JP2005314524A (en) * | 2004-04-28 | 2005-11-10 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated sheet |
| JP2016210860A (en) * | 2015-05-01 | 2016-12-15 | 三菱レイヨン株式会社 | Epoxy resin composition and prepreg for fiber-reinforced composite material |
-
1990
- 1990-02-20 JP JP4051490A patent/JPH03243619A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6620510B1 (en) | 1998-12-25 | 2003-09-16 | Mitsubishi Rayon Co., Ltd. | Epoxy resin composition, prepreg, and roll made of resin reinforced with reinforcing fibers |
| JP2005281488A (en) * | 2004-03-30 | 2005-10-13 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated plate |
| JP2005314524A (en) * | 2004-04-28 | 2005-11-10 | Sumitomo Bakelite Co Ltd | Resin composition, prepreg and laminated sheet |
| JP4569159B2 (en) * | 2004-04-28 | 2010-10-27 | 住友ベークライト株式会社 | Resin composition, prepreg and laminate |
| JP2016210860A (en) * | 2015-05-01 | 2016-12-15 | 三菱レイヨン株式会社 | Epoxy resin composition and prepreg for fiber-reinforced composite material |
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