JP3349556B2 - Epoxy resin composition and prepreg - Google Patents
Epoxy resin composition and prepregInfo
- Publication number
- JP3349556B2 JP3349556B2 JP19371293A JP19371293A JP3349556B2 JP 3349556 B2 JP3349556 B2 JP 3349556B2 JP 19371293 A JP19371293 A JP 19371293A JP 19371293 A JP19371293 A JP 19371293A JP 3349556 B2 JP3349556 B2 JP 3349556B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- bisphenol
- resin
- prepreg
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、比較的低温で硬化する
エポキシ樹脂組成物およびこれらエポキシ樹脂組成物と
補強用繊維とを組み合わせた繊維強化複合材料用プリプ
レグに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition which cures at a relatively low temperature and a prepreg for a fiber-reinforced composite material obtained by combining the epoxy resin composition with a reinforcing fiber.
【０００２】[0002]
【従来の技術】エポキシ樹脂は硬化後の樹脂の機械的特
性、電気的特性に優れるため広い分野に用いられてい
る。例えば、電子材料用封止剤、塗料・舗装材料、ある
いは接着剤と多岐に渡っている。さらに近年、機械特
性、耐熱性に優れることから複合材料用マトリックス樹
脂として用いられるようになってきており、航空機用か
ら釣竿、ゴルフクラブシャフト等の汎用用途まで広く用
いられている。2. Description of the Related Art Epoxy resins have been used in a wide range of fields because of their excellent mechanical and electrical properties after curing. For example, there are a wide variety of materials such as sealants for electronic materials, paints / paving materials, and adhesives. Furthermore, in recent years, it has been used as a matrix resin for composite materials due to its excellent mechanical properties and heat resistance, and has been widely used from aircraft to general-purpose applications such as fishing rods and golf club shafts.
【０００３】この中で一般汎用用途に用いられるプリプ
レグ（マトリックス樹脂と補強繊維とを組み合わせた複
合材料用前駆体）用マトリックス樹脂としては、硬化後
の機械特性に優れることは勿論、プリプレグの室温にお
ける安定性、取扱い性に優れることが要求される。また
成形サイクルの短縮化、エネルギーコストの低減のため
低温硬化、あるいは短時間硬化のマトリックス樹脂に対
する要求が高まっている。これらに対して室温から８０
〜９０℃の低温で硬化する樹脂は既にいくらか存在す
る。しかしこれらのほとんどは硬化直前に主剤と硬化剤
とを混合する、いわゆるハンドレイアップ用の樹脂組成
物であり、室温における安定性は悪く、その可使時間
は、分から時間のオーダーである。また混合直後の樹脂
粘度が低く取扱い性、作業環境とも悪い。これらの欠点
を改良した低温硬化し、かつ現行１３０℃硬化マトリッ
クス樹脂と同様にホットメルトフィルム法によるプリプ
レグ化が可能なマトリックス樹脂の出現は前記の問題を
すべて解決するものとして大きな期待がかけられてい
る。Among these, matrix resins for prepregs (precursors for composite materials in which a matrix resin and a reinforcing fiber are combined) used for general-purpose applications are, of course, excellent in mechanical properties after curing and of course, at room temperature of prepregs. Excellent stability and handleability are required. Further, there is an increasing demand for a matrix resin which is cured at a low temperature or cured for a short time in order to shorten the molding cycle and reduce the energy cost. From room temperature to 80
Some resin already cures at low temperatures of の 90 ° C. However, most of them are so-called hand lay-up resin compositions in which a main agent and a curing agent are mixed immediately before curing, and have poor stability at room temperature, and their pot life is on the order of minutes to hours. In addition, the viscosity of the resin immediately after mixing is low, and the handling properties and working environment are poor. The emergence of a matrix resin that can be cured at a low temperature with these disadvantages improved and that can be prepregged by the hot melt film method like the current 130 ° C. cured matrix resin is expected to solve all of the above problems. I have.
【０００４】これらの要求に対応しようとする手段とし
て、特開昭６１−４３６１６号公報には、エポキシ樹脂
と２塩基酸ジヒドラジド化合物、尿素化合物および融点
が５０℃以上のアルコール系、フェノール系化合物との
組み合わせが開示されている。これらのエポキシ樹脂化
合物は３０℃での安定性は１４日以上あるが、硬化温度
が９０℃以下では硬化不良のため実用上用いることはで
きない。As a means for meeting these demands, Japanese Patent Application Laid-Open No. 61-43616 discloses an epoxy resin, a dibasic acid dihydrazide compound, a urea compound and an alcohol or phenol compound having a melting point of 50 ° C. or more. Are disclosed. These epoxy resin compounds have a stability at 30 ° C. of 14 days or more, but cannot be used practically at a curing temperature of 90 ° C. or less due to poor curing.
【０００５】また、特開平１−１２９０８４号公報には
エポキシ樹脂、ビスフェノールＡとビスフェノールＡの
モノグリシジルエーテルとの反応生成物、および硬化剤
兼硬化促進剤であるイミダゾール化合物から成る樹脂接
着剤が開示されている。しかし、この樹脂組成物をマト
リックス樹脂とする炭素繊維強化樹脂（ＣＦＲＰ）特性
は一方向ＣＦＲＰ０°方向曲げ強度ＦＳ//＝１．２７Ｇ
Ｐａ，ＩＬＳＳ＝７６ＭＰａと、現行１３０℃硬化の汎
用用途に用いられているＣＦＲＰ特性ＦＳ//＝１．７６
ＧＰａ，ＩＬＳＳ＝９８ＧＰａと比較して極端に低い。
また、この樹脂組成物は樹脂調製時に粘度上昇が大き
く、ホットメルトフィルム化が困難である。Japanese Patent Application Laid-Open No. 1-129084 discloses a resin adhesive comprising an epoxy resin, a reaction product of bisphenol A and monoglycidyl ether of bisphenol A, and an imidazole compound which is both a curing agent and a curing accelerator. Have been. However, the carbon fiber reinforced resin (CFRP) using this resin composition as a matrix resin has a unidirectional CFRP 0 ° bending strength FS // = 1.27G.
Pa, ILSS = 76 MPa, CFRP characteristic FS // = 1.76 which is currently used for general purpose curing at 130 ° C.
GPa and ILSS are extremely lower than 98 GPa.
Further, this resin composition has a large increase in viscosity during resin preparation, and it is difficult to form a hot melt film.
【０００６】これら以外にも、Ｐ−ヒドロキシスチレン
を用いた樹脂組成物（特公昭３２−１８５５１号、米国
特許第３、８８４、９９２号）、あるいは三フッ化ホウ
素錯体を用いた樹脂組成物（欧州特許公告第１６５、２
３０号）等が報告されているが、いずれも室温における
安定性が悪かったり、硬化に高温長時間を要したりして
要求を十分に満足する樹脂組成物はなかった。Other than these, a resin composition using P-hydroxystyrene (Japanese Patent Publication No. 32-18551, US Pat. No. 3,884,992) or a resin composition using a boron trifluoride complex ( European Patent Publication No. 165, 2
No. 30) and the like, but none of them has sufficient stability at room temperature or requires a high temperature and a long time for curing, and no resin composition sufficiently satisfies the requirements.
【０００７】また最近ではエポキシ樹脂用の優れた潜在
性硬化剤が市販されており、これらの潜在性硬化剤を利
用すれば室温での安定性に優れ、かつ８０℃で硬化する
一液性のエポキシ樹脂組成物を調製することは可能であ
る。しかしこれらの樹脂組成物をプリプレグのマトリッ
クス樹脂として用いる場合、単に一液であれば良いので
はなくて、プリプレグとしての取扱い性（タックやドレ
ープ性）に優れることが重要であり、その取扱い性を適
正化する方法としては樹脂の粘度を調節する方法が一般
的である。しかし８０℃付近の比較的低温域で硬化する
材料の場合、単純に高分子量の固体エポキシ樹脂を導入
する方法では、硬化温度でのエポキシ分子のモビリティ
ーの低下のため反応性が低下してしまい硬化不良を起こ
してしまうことがある。[0007] Recently, excellent latent curing agents for epoxy resins have been marketed. If these latent curing agents are used, they are excellent in stability at room temperature and are one-pack type curable at 80 ° C. It is possible to prepare an epoxy resin composition. However, when these resin compositions are used as a matrix resin for a prepreg, it is important that the prepreg has excellent handleability (tack and drape properties) instead of simply being one liquid. As a method for adjusting the viscosity, a method of adjusting the viscosity of the resin is generally used. However, in the case of a material that cures in a relatively low temperature range around 80 ° C, simply introducing a high-molecular-weight solid epoxy resin reduces the reactivity of epoxy molecules at the curing temperature, resulting in a decrease in reactivity and curing. Failure may occur.
【０００８】また十分な量の硬化剤を添加して硬化不良
を起こさないようにしても、得られたプリプレグから成
形された複合材料は、汎用１３０℃硬化プリプレグから
成形された複合材料に比べて、機械物性、特に９０°方
向の強度や層間剪断強度が低く、構造材料として用いる
には不安が大きかった。[0008] Even if a sufficient amount of a curing agent is added so as not to cause curing failure, the composite material molded from the obtained prepreg can be compared with a composite material molded from a general-purpose 130 ° C cured prepreg. In addition, mechanical properties, particularly the strength in the 90 ° direction and the interlaminar shear strength were low, and there was great anxiety when used as a structural material.
【０００９】[0009]
【発明が解決しようとする課題】本発明者は、室温にお
ける安定性が実用上十分である２０日以上を有し、かつ
８０℃で実用上十分な特性を有するまで硬化し、かつ、
プリプレグ用マトリックス樹脂として用いた場合、複合
材料が８０℃の成形温度で汎用１３０℃硬化タイプ並の
機械物性を有する樹脂組成物の提供を課題とする。SUMMARY OF THE INVENTION The inventor of the present invention has at least 20 days at which the stability at room temperature is practically sufficient, and cures at 80 ° C. until it has practically sufficient characteristics;
When used as a matrix resin for prepreg, it is an object to provide a resin composition in which a composite material has mechanical properties equivalent to those of a general-purpose 130 ° C. curing type at a molding temperature of 80 ° C.
【００１０】[0010]
【課題を解決するための手段】本発明は、上記課題を解
決するために以下の手段を採る。すなわち、本発明は、
（ａ）エポキシ樹脂：１００重量部、（ｂ）ビスフェノ
ール化合物、またはビスフェノール化合物とビスフェノ
ール化合物のモノグリシジルエーテルとの反応生成物：
５〜１００重量部、（ｃ）尿素系エポキシ樹脂硬化剤、
（ｄ）８０℃付近から反応を始める加熱硬化タイプのマ
イクロカプセル型の潜在性硬化剤から成るエポキシ樹脂
組成物、及び上記エポキシ樹脂組成物と強化繊維を組み
合わせた繊維強化複合材料用プリプレグである。本発明
樹脂組成物は、８０℃で硬化可能であり、かつ２５℃プ
リプレグライフが２０日以上と十分な貯蔵安定性を有す
る。また得られるプリプレグを硬化したＣＦＲＰは現行
１３０℃硬化汎用ＣＦＲＰと同等の特性を有する。The present invention employs the following means in order to solve the above-mentioned problems. That is, the present invention
(A) epoxy resin: 100 parts by weight, (b) bisphenol compound, or reaction product of bisphenol compound and monoglycidyl ether of bisphenol compound:
5 to 100 parts by weight, (c) urea epoxy resin curing agent,
(D) An epoxy resin composition comprising a heat-curable microcapsule-type latent curing agent that starts a reaction at around 80 ° C., and a prepreg for a fiber-reinforced composite material obtained by combining the epoxy resin composition with a reinforcing fiber. The resin composition of the present invention can be cured at 80 ° C., and has sufficient storage stability such that the prepreg life at 25 ° C. is 20 days or more. The CFRP obtained by curing the obtained prepreg has properties equivalent to those of the current general-purpose CFRP cured at 130 ° C.
【００１１】本発明に用いられる（ａ）成分であるエポ
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、あるいは
グリシジルアミン型エポキシ樹脂が挙げられる。このう
ち取扱い性、得られるＣＦＲＰ特性あるいは経済性から
バランスのとれたビスフェノールＡ型エポキシ樹脂の使
用が好ましい。また取扱い性の点から液状エポキシ樹脂
と固形状エポキシ樹脂を混合し使用上最適な粘度として
用いること、あるいは前記エポキシ樹脂をゲル化しない
範囲でアミン化合物等と反応させた生成物を用いること
も本発明のより好ましい実施の態様である。The epoxy resin used as the component (a) in the present invention is not particularly limited, and includes bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and glycidylamine type epoxy resin. No. Of these, it is preferable to use a bisphenol A type epoxy resin which is balanced in terms of handleability, obtained CFRP characteristics, or economy. In addition, the liquid epoxy resin and the solid epoxy resin should be mixed and used at an optimum viscosity in use from the viewpoint of handleability, or a product obtained by reacting the epoxy resin with an amine compound or the like to the extent that the epoxy resin does not gel is used. It is a more preferred embodiment of the invention.
【００１２】成分（ｂ）でるあるビスフェノール化合物
とはビスフェノールＡ、ビスフェノールＦ、ビスフェノ
ールＳを示し、これらを単独で用いても、混合して用い
てもいずれでも可能である。またこれらビスフェノール
化合物とビスフェノール化合物のモノグリシジルエーテ
ルとの反応物を用いることがより好ましい。この反応生
成物は容易に合成することが可能である。またダウ・ケ
ミカル・カンパニーからＤＥＨ−８５としてビスフェノ
ールＡとビスフェノールＡモノグリシジルエーテルの反
応物が市販されている。本発明ではこれら化合物を５〜
１００重量部の範囲で用いる。５重量部を越える添加料
では得られる硬化樹脂の伸度が低く得られるＣＦＲＰ特
性にも悪影響を与える。１００重量部未満では樹脂組成
物の低温での硬化性能が下がり好ましくない。The bisphenol compound as the component (b) is bisphenol A, bisphenol F or bisphenol S, and these can be used alone or in combination. It is more preferable to use a reaction product of these bisphenol compounds and a monoglycidyl ether of the bisphenol compound. This reaction product can be easily synthesized. A reaction product of bisphenol A and bisphenol A monoglycidyl ether is commercially available from Dow Chemical Company as DEH-85. In the present invention, these compounds are
Used in the range of 100 parts by weight. If the additive exceeds 5 parts by weight, the resulting cured resin will have a low elongation, which will also adversely affect the CFRP properties obtained. If the amount is less than 100 parts by weight, the curing performance of the resin composition at a low temperature is unpreferably reduced.
【００１３】成分（ｃ）の尿素系エポキシ樹脂硬化剤と
しては特に制限はないが、下記の一般式で示される化合
物が好適に用いられる。The urea epoxy resin curing agent of the component (c) is not particularly limited, but a compound represented by the following general formula is preferably used.
【００１４】[0014]
【化１】 Embedded image
【００１５】また、下記の一般式に示される化合物も好
適に用いられる。Further, compounds represented by the following general formula are also preferably used.
【００１６】[0016]
【化２】 Embedded image
【００１７】成分（ｃ）の添加量に関しても特に制限は
ないが、少なすぎると成分（ｃ）を添加する効果がみら
れず、多すぎるとライフに悪影響を与える。好ましい範
囲としては２〜２０重量部である。There is no particular limitation on the amount of component (c) to be added, but if the amount is too small, the effect of adding component (c) is not observed, and if it is too large, the life is adversely affected. The preferred range is 2 to 20 parts by weight.
【００１８】成分（ｄ）のマイクロカプセル型潜在性硬
化剤は、８０℃付近で反応を開始するものでなければな
らず、その構成は反応性の高い硬化剤をコアとし、少な
くともそのコアである硬化剤が反応するまではエポキシ
樹脂と反応しない材料をシェルとしたものである。この
ようなマイクロカプセル型潜在性硬化剤のコア成分とし
て使用できる硬化剤としては、アミン類、ポリアミド
類、イミダゾール類、尿素類、ヒドラジド類等、あるい
はこれらの化合物のエポキシアダクト等があり、特にイ
ミダゾール類は硬化樹脂の耐熱性に優れるため好まし
い。また、シェル成分としては高分子量のエポキシ樹脂
やポリウレタン樹脂、ポリエチレン、ポリプロピレン、
ポリスチレン、ナイロン、ポリエステル、ポリ塩化ビニ
ル、ポリ塩化ビニリデン等があげられる。このようなマ
イクロカプセル型の潜在性硬化剤として市販されている
ものでは、旭化成のノバキュアＨＸ３７２１、ＨＸ３７
２２、ＨＸ３８７１、ＨＸ３８９１等がある。The microcapsule-type latent curing agent of the component (d) must be capable of initiating a reaction at around 80 ° C., and has a core composed of a highly reactive curing agent and at least the core. The shell is made of a material that does not react with the epoxy resin until the curing agent reacts. Examples of the curing agent that can be used as a core component of such a microcapsule-type latent curing agent include amines, polyamides, imidazoles, ureas, hydrazides, and the like, and epoxy adducts of these compounds, and in particular, imidazole. Are preferred because of the excellent heat resistance of the cured resin. As the shell component, high-molecular-weight epoxy resin or polyurethane resin, polyethylene, polypropylene,
Examples include polystyrene, nylon, polyester, polyvinyl chloride, and polyvinylidene chloride. Commercially available as such a microcapsule-type latent curing agent, Novacure HX3721 and HX37 available from Asahi Kasei Corporation.
22, HX3891 and HX3891.
【００１９】成分（ｄ）の添加量としては特に制限はな
いが、２〜３０重量部が好適である。２重量部未満だと
成分（ｄ）を添加する効果が見られないことがあり、ま
た３０重量部を越えると得られる樹脂組成物の安定性が
低下する場合がある。成分（ｄ）が８０℃付近で反応を
開始するか否かは、例えば成分（ｄ）をビスフェノール
Ａ型エポキシ樹脂（油化シェル社製Ｅｐ８２８等）に適
量混ぜたものを試料とし、示差走査熱量分析（ＤＳＣ）
の８０℃等温測定で反応発熱があるかどうかで判断す
る。The amount of component (d) added is not particularly limited, but is preferably 2 to 30 parts by weight. If the amount is less than 2 parts by weight, the effect of adding the component (d) may not be obtained, and if it exceeds 30 parts by weight, the stability of the obtained resin composition may be reduced. Whether or not the component (d) starts the reaction at around 80 ° C. can be determined, for example, by using a sample obtained by mixing the component (d) with an appropriate amount of a bisphenol A type epoxy resin (such as Ep828 manufactured by Yuka Shell Co., Ltd.) as a sample, Analysis (DSC)
The determination is made based on whether or not there is a reaction exotherm in the 80 ° C. isothermal measurement.
【００２０】これら（ｂ）〜（ｄ）で示される硬化剤は
単独では既に使用されており、それなりの性能を有する
樹脂組成物が得られている。しかし、本発明の目的とす
る低温で硬化して優れた硬化物物性を発揮し、しかも室
温における貯蔵安定性に優れた樹脂組成物は得られてい
なかった。本発明のように、上記３つの硬化剤を用いる
ことによりはじめてこれらの目的が達成できたのであ
り、またプリプレグ用樹脂として用いた場合、適度なタ
ック・ドレープ性を発揮することができるのである。か
かる硬化剤および硬化促進剤の選択及び組み合わせが本
発明の骨子である。The curing agents (b) to (d) have already been used alone, and a resin composition having a certain performance has been obtained. However, a resin composition which cures at a low temperature and exhibits excellent cured physical properties and has excellent storage stability at room temperature, which is the object of the present invention, has not been obtained. These objects can be achieved for the first time by using the above three curing agents as in the present invention, and when used as a resin for prepreg, an appropriate tack and drape property can be exhibited. The selection and combination of such a curing agent and a curing accelerator are the gist of the present invention.
【００２１】また本発明の樹脂組成物には成形時の流れ
性、タック等を改良するために、硬化性、保存安定性に
影響を与えない程度に熱可塑性樹脂を添加してもかまわ
ない。添加形態も溶解、分散のいずれでも良い。このよ
うな熱可塑性樹脂としては例えばポリビニルホルマー
ル、ポリエーテルスルホン、ポリスルホン、ポリアリレ
ート、ポリアミド、ポリパラバン酸、フェノキシ樹脂等
があげられる。In order to improve the flowability and tackiness during molding, a thermoplastic resin may be added to the resin composition of the present invention to such an extent that the curability and storage stability are not affected. The addition form may be either dissolution or dispersion. Examples of such a thermoplastic resin include polyvinyl formal, polyether sulfone, polysulfone, polyarylate, polyamide, polyparabanic acid, and phenoxy resin.
【００２２】以上説明した本発明の樹脂組成物と組み合
わせて繊維強化複合材料用プリプレグを得るための補強
用繊維としては、炭素繊維、ガラス繊維、アラミド繊維
等が挙げられるが、特に制限されるものではない。本発
明のエポキシ樹脂組成物は前述のごとく優れた安定性を
有するため樹脂を加熱して離型紙上に樹脂の薄膜を形成
する、いわゆるホットメルトフィルムが安定に調整可能
である。このため従来の低温硬化樹脂では不可能であっ
たホットメルト法によるプリプレグの製造が可能とな
る。このことはこれまでの低温硬化樹脂において一般的
であったハンドレイアップ法、あるいは溶剤を用いるラ
ッカー法によらないプリプレグの製造が可能となり、経
済的にも作業環境的にも非常に有利となる。Examples of reinforcing fibers for obtaining a prepreg for a fiber-reinforced composite material in combination with the above-described resin composition of the present invention include carbon fibers, glass fibers, and aramid fibers, but are not particularly limited. is not. Since the epoxy resin composition of the present invention has excellent stability as described above, a so-called hot melt film, which forms a thin film of resin on release paper by heating the resin, can be stably adjusted. For this reason, it becomes possible to manufacture a prepreg by a hot melt method, which is impossible with a conventional low-temperature curing resin. This makes it possible to manufacture prepregs that are not based on the hand lay-up method or the lacquer method using a solvent, which has been common in conventional low-temperature curing resins, which is very advantageous both economically and in terms of working environment. .
【００２３】[0023]
【実施例】以下実施例により本発明をさらに詳しく説明
する。実施例中の化合物の略号、及び試験法は以下の通
りである。なお、硬化成形条件は特別な記述がない限り
すべて８０℃×５時間とした。 Ｅｐ８２８ ：ビスフェノールＡ型エポキシ樹脂（油
化シェル社製） Ｅｐ１００１ ：ビスフェノールＡ型エポキシ樹脂（油
化シェル社製） ＤＥＨ−８５ ：ビスフェノールＡ変性硬化剤（ダウケ
ミカル社製） ＤＣＭＵ ：３，４−ジクロルフェニル−Ｎ，Ｎ−
ジメチル尿素 オミキュア９４：３−フェニル−１、１ジメチルウレア
（ＡＣＩ Ｊａｐａｎ社製）The present invention will be described in more detail with reference to the following examples. Abbreviations of compounds in the examples and test methods are as follows. The curing molding conditions were all 80 ° C. × 5 hours unless otherwise specified. Ep828: Bisphenol A type epoxy resin (manufactured by Yuka Shell) Ep1001: Bisphenol A type epoxy resin (manufactured by Yuka Shell) DEH-85: Bisphenol A modified curing agent (manufactured by Dow Chemical Company) DCMU: 3,4-di Chlorphenyl-N, N-
Dimethylurea Omicure 94: 3-phenyl-1, 1-dimethylurea (manufactured by ACI Japan)
【００２４】[0024]
【化３】 Embedded image
【００２５】オミキュア２４：１，１’−４（メチル−
ｍ−フェニレン）ビス（３，３’ジメチルウレア）
（ＡＣＩ Ｊａｐａｎ社製）Omicure 24: 1, 1'-4 (methyl-
m-phenylene) bis (3,3′dimethylurea)
(Manufactured by ACI Japan)
【００２６】[0026]
【化４】 Embedded image
【００２７】ＨＸ３７２２ ：マイクロカプセル型潜在
性硬化剤（旭化成社製） ｍ−ＰＤＡ ：メタ−フェニレンジアミン ＸＤＡ ：キシレンジアミン ＰＡ ：無水フタル酸 ＰＭＭＡ ：ポリメタクリル酸メチルHX3722: microcapsule type latent curing agent (manufactured by Asahi Kasei Corporation) m-PDA: meta-phenylenediamine XDA: xylenediamine PA: phthalic anhydride PMMA: polymethyl methacrylate
【００２８】＜硬化樹脂曲げ試験（３点曲げ）＞ 装置 ：オリエンテック製 テンシロン サンプル形状、Ｌ／Ｄ（＝支点間距離／厚み） ：樹脂板 長さ60mm，幅８mm，厚さ２mm，Ｌ／
Ｄ＝16 ：ＣＦＲＰ ０° 長さ120mm,幅10mm，厚さ２mm，Ｌ／
Ｄ＝40 ：ＣＦＲＰ 90° 長さ60mm, 幅10mm，厚さ２mm，Ｌ／
Ｄ＝16 ＩＬＳＳ 長さ30mm, 幅10mm，厚さ４mm，Ｌ／Ｄ＝４ 圧子先端半径 ：3.2mm CROSS HEAD SPEED ：２mm／min<Cured resin bending test (3-point bending)> Apparatus: Orientec Tensilon sample shape, L / D (= distance between supports / thickness): resin plate 60 mm long, 8 mm wide, 2 mm thick, L / D
D = 16: CFRP 0 ° length 120mm, width 10mm, thickness 2mm, L /
D = 40: CFRP 90 ° 60mm in length, 10mm in width, 2mm in thickness, L /
D = 16 ILSS Length 30mm, Width 10mm, Thickness 4mm, L / D = 4 Indenter tip radius: 3.2mm CROSS HEAD SPEED: 2mm / min
【００２９】＜硬化樹脂粘弾性特性＞ 装置 ：レオメトリックス製 ＲＤＡ−７００ サンプル形状 ：長さ60mm，幅12mm，厚さ２mm 昇温条件 ：１℃／min 変形速度 ：6.28 rad/sec（＝１Hz）<Curing resin viscoelastic properties> Apparatus: RDA-700 manufactured by Rheometrics Sample shape: length 60 mm, width 12 mm, thickness 2 mm Heating condition: 1 ° C / min Deformation rate: 6.28 rad / sec (= 1 Hz)
【００３０】＜硬化発熱測定＞ 装置 ：デュポン製 ９１０−ＤＳＣ 測定条件 ：等温測定<Measurement of Exothermic Curing> Apparatus: 910-DSC made by DuPont Measurement conditions: Isothermal measurement
【００３１】［予備調製１］コア成分としてｍ−ＰＤＡ
を用い、ＰＭＭＡをシェル成分としてマイクロカプセル
化した。このマイクロカプセル型硬化剤をｄ−１とす
る。[Preparation 1] m-PDA as a core component
And PMMA was microencapsulated as a shell component. This microcapsule type curing agent is designated as d-1.
【００３２】［予備反応２］コア成分としてＸＤＡを用
い、ＰＭＭＡをシェル成分としてマイクロカプセル化し
た。このマイクロカプセル型硬化剤をｄ−２とする。[Preliminary Reaction 2] XDA was used as a core component, and PMMA was microencapsulated as a shell component. This microcapsule type curing agent is referred to as d-2.
【００３３】［予備反応３］コア成分としてＰＡを用
い、ＰＭＭＡをシェル成分としてマイクロカプセル化し
た。このマイクロカプセル型硬化剤をｄ−３とする。[Preliminary Reaction 3] PA was used as a core component, and PMMA was microencapsulated as a shell component. This microcapsule type curing agent is referred to as d-3.
【００３４】［実施例１］エポキシ樹脂Ｅｐ１００１：
３０重量部、Ｅｐ８２８：７０重量部、及びフェノール
系硬化剤ＤＥＨ−８５：６０重量部を、９０℃に加熱し
たニーダーに投入して均一に混合した。ニーダー加熱温
度を５５℃に冷却、樹脂温度も低下したことを確認した
後、オミキュア９４を１０重量部、ＨＸ３７２２を５重
量部添加して混合し均一な樹脂組成物を得た。この樹脂
組成物を厚さ２ｍｍのテフロン板をスペーサーとするガ
ラスセルの間に流し込んで表１に示す硬化条件で成形
し、透明な硬化樹脂を得た。この樹脂板を用いて曲げ試
験、粘弾性測定を実施した。結果を併せて表１に示す。
また、ＨＸ３７２２の８０℃での硬化性を確認するた
め、Ｅｐ８２８：１００重量部に対して３０重量部の組
成物を調製し、８０℃での硬化発熱を測定したところ、
硬化発熱がみられＨＸ３７２２が８０℃で硬化すること
を確認した。Example 1 Epoxy resin Ep1001:
30 parts by weight, 70 parts by weight of Ep828, and 60 parts by weight of a phenolic curing agent DEH-85 were charged into a kneader heated to 90 ° C. and uniformly mixed. After cooling the kneader heating temperature to 55 ° C. and confirming that the resin temperature also dropped, 10 parts by weight of Omicure 94 and 5 parts by weight of HX3722 were added and mixed to obtain a uniform resin composition. This resin composition was poured into a glass cell having a Teflon plate having a thickness of 2 mm as a spacer and molded under the curing conditions shown in Table 1 to obtain a transparent cured resin. Using this resin plate, a bending test and a viscoelasticity measurement were performed. The results are shown in Table 1.
Further, in order to confirm the curability of HX3722 at 80 ° C., 30 parts by weight of a composition was prepared with respect to 100 parts by weight of Ep828, and the curing heat generation at 80 ° C. was measured.
It was confirmed that HX3722 was cured at 80 ° C. due to heat generation during curing.
【００３５】[0035]
【表１】 [Table 1]
【００３６】［実施例２］実施例１で得られた樹脂組成
物（硬化前）と炭素繊維（三菱レイヨン社製 パイロフ
ィルＴＲ−４０）とから一方向プリプレグをホットメル
ト法で製造した。フィルム化温度は５０℃、炭素繊維へ
の含浸は７０℃で実施した。このプリプレグは適当なタ
ックとドレープ性を有しており、２５℃で１カ月保管し
た後もタックやドレープ性に変化は少なく、良好な貯蔵
安定性を有していた。なお、タック及びドレープ性の評
価は、直径８ｍｍの鉛筆にプリプレグを巻き付け、プリ
プレグの割れや巻き戻りが起こらないことを確認し、良
否の判定を行った。このプリプレグを一方向に約２ｍｍ
厚に積層し、真空成形により成形した。得られた一方向
ＣＦＲＰのＶf （ＣＦの体積含有率）＝６０％であり、
０°、９０°の曲げ、ＩＬＳＳ試験を実施した結果、０
°方向：ＦＳ//＝１８４ｋｇ／ｍｍ2 、９０°方向：Ｆ
Ｓ⊥＝１０．４ｋｇ／ｍｍ2 、ＩＬＳＳ＝８．９ｋｇ／
ｍｍ2 であった。Example 2 A unidirectional prepreg was produced from the resin composition (before curing) obtained in Example 1 and carbon fibers (Pyrofil TR-40 manufactured by Mitsubishi Rayon Co., Ltd.) by a hot melt method. The film formation temperature was 50 ° C., and the impregnation into the carbon fiber was 70 ° C. This prepreg had appropriate tack and drape properties, and showed little change in tack and drape properties even after storage at 25 ° C. for one month, and had good storage stability. The evaluation of tackiness and drapability was performed by wrapping a prepreg around a pencil having a diameter of 8 mm, confirming that the prepreg did not crack or unwound, and evaluated the quality. This prepreg is about 2mm in one direction
It was laminated to a thickness and formed by vacuum forming. Vf (volume content of CF) of the obtained one-way CFRP is 60%,
As a result of performing a 0 ° and 90 ° bending and ILSS test,
° direction: FS // = 184 kg / mm 2 , 90 ° direction: F
S⊥ = 10.4 kg / mm 2 , ILSS = 8.9 kg /
mm 2 .
【００３７】[0037]
【表２】 [Table 2]
【００３８】［実施例３、比較例１］ＤＥＨ−８５量を
表２の如く変えた以外は実施例１、及び２と同様にして
樹脂組成物を調製、硬化して硬化樹脂、及び一方向ＣＦ
ＲＰを作成した。樹脂及びＣＦＲＰの機械特性を評価
し、得られた結果を表２に併せて示した。Example 3, Comparative Example 1 A resin composition was prepared and cured in the same manner as in Examples 1 and 2 except that the amount of DEH-85 was changed as shown in Table 2, and a cured resin, and one-way CF
RP was created. The mechanical properties of the resin and CFRP were evaluated, and the obtained results are shown in Table 2.
【００３９】［実施例４、５］実施例１、及び２の成分
（ｃ）の、オミキュア９４：１０重量部を、ＤＣＭＵ：
１０重量部（実施例４）、およびオミキュア２４：１０
重量部（実施例５）に変えた以外は実施例１、及び２と
同様にして樹脂組成物を調製、硬化して、硬化樹脂、及
び一方向ＣＦＲＰを形成した。得られた結果を表３に示
した。[Examples 4 and 5] 94:10 parts by weight of Omicure of the component (c) of Examples 1 and 2 were added to DCMU:
10 parts by weight (Example 4), and Omicure 24:10
A resin composition was prepared and cured in the same manner as in Examples 1 and 2 except that the amount was changed to parts by weight (Example 5) to form a cured resin and a one-way CFRP. Table 3 shows the obtained results.
【００４０】［実施例６、７、比較例２］実施例１、及
び２の成分（ｄ）のＨＸ３７２２：５重量部を予備反応
１〜３でそれぞれ得られたｄ−１（実施例６）、ｄ−２
（実施例７）、ｄ−３（比較例２）：各５重量部に変え
た以外は実施例１、及び２と同様にして樹脂組成物を調
製、硬化して、硬化樹脂、及び一方向ＣＦＲＰを形成し
た。得られた結果を表３に示した。また、ｄ−１、ｄ−
２、ｄ−３それぞれの８０℃での硬化性を確認するた
め、Ｅｐ８２８：１００重量部に対して３０重量部の組
成物をそれぞれ調製し、８０℃での硬化発熱を測定した
ところ、ｄ−１、ｄ−２は８０℃で硬化したがｄ−３は
硬化しなかった。[Examples 6 and 7, Comparative Example 2] d-1 in which 5 parts by weight of HX3722 of the component (d) of Examples 1 and 2 were obtained by preliminary reactions 1 to 3, respectively (Example 6) , D-2
(Example 7), d-3 (Comparative Example 2): A resin composition was prepared and cured in the same manner as in Examples 1 and 2 except that each was changed to 5 parts by weight, and a cured resin and one-way CFRP was formed. Table 3 shows the obtained results. Also, d-1, d-
In order to confirm the curability at 80 ° C. of each of d and d-3, 30 parts by weight of a composition was prepared with respect to 100 parts by weight of Ep828, and the exothermic curing at 80 ° C. was measured. 1, d-2 was cured at 80 ° C., but d-3 was not cured.
【００４１】[0041]
【表３】 [Table 3]
【００４２】[0042]
【発明の効果】本発明の樹脂組成物を用いると、８０℃
で実用上十分な程度に硬化する。また本発明の樹脂を用
いたホットメルトフィルム法によるＣＦＲＰ用プリプレ
グは室温で２０日以上という実用上十分な安定性、並び
に適度なタック・ドレープ性を有しており、得られるＣ
ＦＲＰの機械物性も現行１３０℃硬化品と同等の性能を
示す。更に、本発明の樹脂組成物は、生産上、経済上、
あるいは近年特に問題となっている作業環境の問題にお
いても従来の低温硬化エポキシ樹脂組成物に比べて大き
な特徴を有している。このためこれまで硬化条件、プリ
プレグの室温安定性、あるいは作業環境上使用されてい
なかった分野への用途が期待される。When the resin composition of the present invention is used, a temperature of 80.degree.
Cures to a practically sufficient degree. Further, the prepreg for CFRP by the hot melt film method using the resin of the present invention has practically sufficient stability of 20 days or more at room temperature, and has an appropriate tack and drape property.
The mechanical properties of FRP also show the same performance as the current 130 ° C cured product. Furthermore, the resin composition of the present invention is economical in production,
Alternatively, it has a great feature in comparison with the conventional low-temperature-curable epoxy resin composition even in the problem of the working environment, which has become a particular problem in recent years. For this reason, it is expected to be used in fields that have not been used in curing conditions, room temperature stability of prepreg, or work environment.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平４−325518（ＪＰ，Ａ) 特開 昭62−174221（ＪＰ，Ａ) 特開 平６−322068（ＪＰ，Ａ) 特開 昭61−43616（ＪＰ，Ａ) 特開 平１−129084（ＪＰ，Ａ) 特開 平６−9758（ＪＰ，Ａ) 特開 平５−310890（ＪＰ，Ａ) 特開 平２−292325（ＪＰ，Ａ) 特開 昭53−125475（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 59/40 - 59/62 C08J 5/24 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-325518 (JP, A) JP-A-62-174221 (JP, A) JP-A-6-322068 (JP, A) JP-A 61-174 43616 (JP, A) JP-A-1-129084 (JP, A) JP-A-6-9758 (JP, A) JP-A-5-310890 (JP, A) JP-A-2-292325 (JP, A) JP-A-53-125475 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 59/40-59/62 C08J 5/24
Claims (5)
合物とビスフェノール化合物のモノグリシジルエーテル
との反応生成物：５〜１００重量部 （ｃ）尿素系エポキシ樹脂硬化剤 （ｄ）８０℃付近から反応を始める加熱硬化タイプのマ
イクロカプセル型の潜在性硬化剤 から成るエポキシ樹脂組成物。(A) epoxy resin: 100 parts by weight (b) bisphenol compound or reaction product of bisphenol compound and monoglycidyl ether of bisphenol compound: 5 to 100 parts by weight (c) urea-based epoxy resin curing agent (D) An epoxy resin composition comprising a heat-curable microcapsule-type latent curing agent which starts a reaction at around 80 ° C.
００を有する液状ビスフェノール型エポキシ樹脂と、エ
ポキシ当量４００〜４０００を有する固形ビスフェノー
ル型エポキシ樹脂との混合物である請求項１記載のエポ
キシ樹脂組成物。2. An epoxy resin having an epoxy equivalent of 170 to 2
The epoxy resin composition according to claim 1, wherein the epoxy resin composition is a mixture of a liquid bisphenol-type epoxy resin having a molecular weight of 00 and a solid bisphenol-type epoxy resin having an epoxy equivalent of 400 to 4000.
とビスフェノールＡのモノグリシジルエーテルとの反応
生成物である請求項１記載のエポキシ樹脂組成物。3. The curing agent of component (b) is bisphenol A
The epoxy resin composition according to claim 1, wherein the epoxy resin composition is a reaction product of bisphenol A and a monoglycidyl ether of bisphenol A.
（ｅ）補強繊維に含浸して得られるプリプレグ。4. A prepreg obtained by impregnating (e) a reinforcing fiber with the epoxy resin composition according to claim 1.
用いる請求項４記載のプリプレグ。5. The prepreg according to claim 4, wherein a carbon fiber is used as the reinforcing fiber of the component (e).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19371293A JP3349556B2 (en) | 1993-06-08 | 1993-08-04 | Epoxy resin composition and prepreg |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-137593 | 1993-06-08 | ||
| JP13759393 | 1993-06-08 | ||
| JP19371293A JP3349556B2 (en) | 1993-06-08 | 1993-08-04 | Epoxy resin composition and prepreg |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0753673A JPH0753673A (en) | 1995-02-28 |
| JP3349556B2 true JP3349556B2 (en) | 2002-11-25 |
Family
ID=26470848
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19371293A Expired - Lifetime JP3349556B2 (en) | 1993-06-08 | 1993-08-04 | Epoxy resin composition and prepreg |
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| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2794735B1 (en) | 2011-12-22 | 2019-07-17 | Hexcel Holding GmbH | Improvements in or relating to fibre reinforced composites |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53125475A (en) * | 1977-04-08 | 1978-11-01 | Mitsubishi Rayon Co Ltd | Prepreg |
| JPS6143616A (en) * | 1984-08-08 | 1986-03-03 | Toho Rayon Co Ltd | Epoxy resin composition |
| JPS62174221A (en) * | 1986-01-27 | 1987-07-31 | Matsushita Electric Works Ltd | One-component epoxy resin composition |
| US4777084A (en) * | 1987-10-08 | 1988-10-11 | Minnesota Mining And Manufacturing Company | Phenolic-modified epoxy adhesive including the reaction product of bisphenol A and the monoglycidyl ether of bisphenol A |
| JPH02292325A (en) * | 1989-05-02 | 1990-12-03 | Nitto Denko Corp | Epoxy resin composition prepared by using microencapsulated amine curing agent |
| JPH04325518A (en) * | 1991-04-25 | 1992-11-13 | Tonen Corp | Epoxy resin composition |
| JP3342710B2 (en) * | 1992-05-12 | 2002-11-11 | 三菱レイヨン株式会社 | Epoxy resin composition and prepreg for composite material therefrom |
| JPH069758A (en) * | 1992-06-23 | 1994-01-18 | Mitsubishi Rayon Co Ltd | Epoxy resin composition |
| JP3479782B2 (en) * | 1993-05-10 | 2003-12-15 | 三菱レイヨン株式会社 | Low temperature curing epoxy resin composition for prepreg |
-
1993
- 1993-08-04 JP JP19371293A patent/JP3349556B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2794735B1 (en) | 2011-12-22 | 2019-07-17 | Hexcel Holding GmbH | Improvements in or relating to fibre reinforced composites |
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| JPH0753673A (en) | 1995-02-28 |
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