JP2003002953A - Epoxy resin composition and fiber-reinforced resin composite material - Google Patents
Epoxy resin composition and fiber-reinforced resin composite materialInfo
- Publication number
- JP2003002953A JP2003002953A JP2002115447A JP2002115447A JP2003002953A JP 2003002953 A JP2003002953 A JP 2003002953A JP 2002115447 A JP2002115447 A JP 2002115447A JP 2002115447 A JP2002115447 A JP 2002115447A JP 2003002953 A JP2003002953 A JP 2003002953A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- curing agent
- mass
- amine
- 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.)
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Links
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- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特に繊維強化樹脂
複合材料のマトリックス樹脂として好適に用いられるエ
ポキシ樹脂組成物に関するものである。TECHNICAL FIELD The present invention relates to an epoxy resin composition which is preferably used as a matrix resin for a fiber-reinforced resin composite material.
【０００２】[0002]
【従来の技術】繊維強化複合材料（以下、ＦＲＰと記
す）は、スポーツ・レジャー関連から航空機用途まで広
く用いられている。このＦＲＰを成形するには、一般に
熱硬化性マトリックス樹脂組成物を補強材に含浸してな
るプリプレグを積層し、加熱・加圧して成形する。このプ
リプレグに使用されるマトリックス樹脂組成物の代表的
なものとして、エポキシ樹脂組成物がある。エポキシ樹
脂組成物は、補強材との接着性や、硬化性、硬化後の機
械物性、取り扱い性等、様々な特性のバランスに非常に
優れているが、これはエポキシ樹脂組成物を構成するエ
ポキシ樹脂と硬化剤に非常に多くの種類が存在している
ことによる。特にエポキシ樹脂の種類は多く、それらを
混合することにより、エポキシ樹脂組成物は様々な特性
を得ることができる。例えば、耐熱性を要求される場合
には、三官能以上の多官能エポキシ樹脂を混合すればよ
いし、プリプレグ用のマトリックス樹脂組成物として適
正な粘度レベルが要求される場合には、固形のエポキシ
樹脂と液状のエポキシ樹脂を適当に混ぜればよい。とこ
ろで近年、ＦＲＰは工業用途に多く用いられるようにな
ってきており、スポーツ・レジャー用途に用いられるＦ
ＲＰに比べて、耐熱性が要求されることが多くなってき
た。2. Description of the Related Art Fiber reinforced composite materials (hereinafter referred to as "FRP") are widely used for sports / leisure and aircraft applications. In order to mold this FRP, generally, a prepreg obtained by impregnating a thermosetting matrix resin composition into a reinforcing material is laminated, and heated and pressed to mold it. An epoxy resin composition is a typical example of the matrix resin composition used for this prepreg. Epoxy resin composition is very excellent in the balance of various properties such as adhesiveness with reinforcing material, curability, mechanical properties after curing, handling property, etc. Due to the existence of so many types of resins and hardeners. Especially, there are many kinds of epoxy resins, and by mixing them, the epoxy resin composition can obtain various properties. For example, when heat resistance is required, a trifunctional or higher polyfunctional epoxy resin may be mixed, and when a proper viscosity level is required as a matrix resin composition for prepreg, a solid epoxy resin is used. The resin and the liquid epoxy resin may be mixed appropriately. By the way, in recent years, FRP has been widely used for industrial purposes, and FRP used for sports / leisure purposes.
In many cases, heat resistance is required as compared with RP.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上述し
たように、耐熱性が要求される場合には三官能以上の多
官能エポキシ樹脂を混ぜればよいが、一般的に耐熱性を
向上させた場合には吸水率が高くなり、耐熱水性が悪く
なる。これは多官能エポキシ樹脂を導入し、硬化物の架
橋密度が上がることによって耐熱性は向上するが、一方
で架橋密度が上がると自由体積が大きくなるため、吸水
率が大きくなるからといわれている。代表的な多官能エ
ポキシ樹脂としては、テトラグリシジルジアミノジフェ
ニルメタン（以下、ＴＧＤＤＭと略記する）がある。こ
のＴＧＤＤＭは、耐熱性の向上に非常に大きな効果があ
り、耐熱用途のマトリックス樹脂として良く用いられる
が、硬化物の耐熱水性はあまり良くない。また、硬化剤
としては、芳香族アミン系硬化剤が耐熱性向上に効果が
あり、特にジアミノジフェニルスルホン（以下、ＤＤＳ
と略記する）が、耐熱用マトリックス樹脂の硬化剤とし
て良く用いられている。しかしながら、このＤＤＳを用
いた硬化物も、耐熱性は向上するものの、吸水性が高く
なり耐熱水性は高くはなかった。However, as described above, when heat resistance is required, a polyfunctional epoxy resin having three or more functional groups may be mixed, but in general, when heat resistance is improved, Has a high water absorption rate and poor hot water resistance. It is said that heat resistance is improved by introducing a polyfunctional epoxy resin and increasing the crosslink density of the cured product, but on the other hand, when the crosslink density is increased, the free volume is increased and the water absorption rate is increased. . A typical polyfunctional epoxy resin is tetraglycidyl diaminodiphenylmethane (hereinafter abbreviated as TGDDM). This TGDDM has a very large effect on improving heat resistance and is often used as a matrix resin for heat resistance, but the hot water resistance of the cured product is not so good. As a curing agent, an aromatic amine-based curing agent is effective in improving heat resistance, and particularly diaminodiphenyl sulfone (hereinafter referred to as DDS).
Is abbreviated) is often used as a curing agent for the heat-resistant matrix resin. However, the cured product using this DDS also has improved heat resistance, but its water absorption is high, and its hot water resistance is not high.
【０００４】本発明の課題は、耐熱性が良好であり、か
つ吸水率が低く、耐熱水性の良好な硬化物を得ることが
できるエポキシ樹脂組成物、及びそれを含有する繊維強
化樹脂複合材料を提供することである。An object of the present invention is to provide an epoxy resin composition having a good heat resistance, a low water absorption rate, and a cured product having a good hot water resistance, and a fiber-reinforced resin composite material containing the same. Is to provide.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
に、本発明のエポキシ樹脂組成物は、エポキシ樹脂
（Ａ）、アミン系硬化剤（Ｂ）、ルイス酸錯体（Ｃ）を
含有するエポキシ樹脂組成物で、アミン系硬化剤（Ｂ）
の添加量が、エポキシ樹脂（Ａ）に対する化学量論量の
１０質量％以上、７０質量％以下であることを特徴とす
る。また、上記エポキシ樹脂（Ａ）が、クレゾールノボ
ラック型エポキシ樹脂、あるいは下記構造式（i）、（i
i）、（iii）で表されるノボラック型のエポキシ樹脂の
うち、少なくとも一つを含むことが望ましい。更に、エ
ポキシ樹脂（Ａ）全体に対して、ノボラック型のエポキ
シ樹脂を４０質量％以上含むことが望ましい。In order to solve the above problems, the epoxy resin composition of the present invention is an epoxy resin containing an epoxy resin (A), an amine curing agent (B) and a Lewis acid complex (C). Resin composition, amine curing agent (B)
Is added in an amount of 10% by mass or more and 70% by mass or less of the stoichiometric amount with respect to the epoxy resin (A). The epoxy resin (A) is a cresol novolac type epoxy resin, or the following structural formulas (i) and (i
It is desirable to contain at least one of the novolac type epoxy resins represented by i) and (iii). Further, it is desirable that the novolac type epoxy resin is contained in an amount of 40% by mass or more based on the whole epoxy resin (A).
【化４】 ｎは０以上の数[Chemical 4] n is a number greater than or equal to 0
【化５】 ｎは０以上の数[Chemical 5] n is a number greater than or equal to 0
【化６】
ｎは０以上の数
また、上記アミン系硬化剤（Ｂ）の添加量が、エポキシ
樹脂（Ａ）の全体に対して、化学量論量の２０質量％以
上であることが好ましい。また、上記アミン系硬化剤
（Ｂ）の添加量が、エポキシ樹脂（Ａ）の全体に対し
て、化学量論量の６０質量％以下であることが好まし
い。また、上記アミン系硬化剤（Ｂ）として、芳香族ア
ミンを用いることが好ましい。また、上記芳香族アミン
が、ジアミノジフェニルスルホンであることが好まし
い。また、上記ルイス酸錯体（Ｃ）として、三弗化硼素
のアミン錯体を用いることが好ましい。本発明のエポキ
シ樹脂組成物は、繊維強化樹脂複合材料のマトリックス
樹脂として好適に用いられる。[Chemical 6] n is a number of 0 or more, and the addition amount of the amine-based curing agent (B) is preferably 20 mass% or more of the stoichiometric amount with respect to the entire epoxy resin (A). Further, the addition amount of the amine curing agent (B) is preferably 60% by mass or less of the stoichiometric amount with respect to the entire epoxy resin (A). Moreover, it is preferable to use an aromatic amine as the amine curing agent (B). Further, it is preferable that the aromatic amine is diaminodiphenyl sulfone. Moreover, it is preferable to use an amine complex of boron trifluoride as the Lewis acid complex (C). The epoxy resin composition of the present invention is suitably used as a matrix resin for a fiber-reinforced resin composite material.
【０００６】[0006]
【発明の実施の形態】本発明は、エポキシ樹脂（Ａ）、
アミン系硬化剤（Ｂ）、ルイス酸錯体（Ｃ）を含有する
エポキシ樹脂組成物である。上記エポキシ樹脂（Ａ）と
しては、特に制限はなく、ビスフェノールＡ型、ビスフ
ェノールＦ型、ビスフェノールＳ型、フェノールノボラ
ック型、クレゾールノボラック型、脂環式等かなるエポ
キシ樹脂も使用可能である。また、エポキシ樹脂（Ａ）
は、クレゾールノボラック型エポキシ樹脂、または下記
構造式（i）、（ii）、（iii）で表されるエポキシ樹脂
のうち、少なくともいずれか一つを含むことが、耐熱性
と吸水性のバランスにおいて好ましい。クレゾールノボ
ラック型エポキシ樹脂としては、ジャパンエポキシレジ
ン社製のエピコート１８０Ｓ６５、大日本インキ化学工
業社製のエピクロンＮ−６００シリーズ等が例示でき
る。また、構造式（i）で表されるエポキシ樹脂として
は、エピクロンＨＰ−７２００が例示でき、構造式（i
i）で表されるエポキシ樹脂としては、ジャパンシェル
エポキシ社製のエピコート１０３２Ｈ６０やチバガイギ
ー社製のＴＡＣＴＩＸ７４２等が例示でき、構造式（ii
i）で表されるエポキシ樹脂としては、ジャパンシェル
エポキシ社製のエピコート１５７Ｓ７０が例示できる。
また、クレゾールノボラック型エポキシ樹脂、または構
造式（i）、（ii）、（iii）で表されるエポキシ樹脂の
含有量が、エポキシ樹脂（Ａ）全体に対して４０質量％
以上であることが耐熱性を向上する点で好ましい。ま
た、構造式（ii）で表されるエポキシ樹脂の含有量が、
エポキシ樹脂（Ａ）全体に対して５０質量％以上である
と、耐熱性が更に良好になり、且つ吸水後の耐熱性の低
下が極めて少ない点で特に好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to an epoxy resin (A),
An epoxy resin composition containing an amine-based curing agent (B) and a Lewis acid complex (C). The epoxy resin (A) is not particularly limited, and epoxy resins such as bisphenol A type, bisphenol F type, bisphenol S type, phenol novolac type, cresol novolac type, and alicyclic type can also be used. Also, epoxy resin (A)
Is a cresol novolac type epoxy resin or an epoxy resin represented by the following structural formulas (i), (ii), and (iii), in order to balance heat resistance and water absorption. preferable. Examples of the cresol novolac type epoxy resin include Epicoat 180S65 manufactured by Japan Epoxy Resin Co., Ltd., Epicron N-600 series manufactured by Dainippon Ink and Chemicals, Inc., and the like. Further, as the epoxy resin represented by the structural formula (i), Epiclon HP-7200 can be exemplified.
Examples of the epoxy resin represented by i) include Epicoat 1032H60 manufactured by Japan Shell Epoxy Co., Ltd. and TACTIX742 manufactured by Ciba-Geigy Co., Ltd.
Examples of the epoxy resin represented by i) include Epicoat 157S70 manufactured by Japan Shell Epoxy Co., Ltd.
Further, the content of the cresol novolac type epoxy resin or the epoxy resin represented by the structural formulas (i), (ii) and (iii) is 40% by mass based on the whole epoxy resin (A).
The above is preferable in terms of improving heat resistance. Further, the content of the epoxy resin represented by the structural formula (ii) is
When the content is 50% by mass or more based on the whole epoxy resin (A), the heat resistance is further improved, and the decrease in heat resistance after water absorption is extremely small, which is particularly preferable.
【０００７】[0007]
【化７】 ｎは０以上の数[Chemical 7] n is a number greater than or equal to 0
【０００８】[0008]
【化８】 ｎは０以上の数[Chemical 8] n is a number greater than or equal to 0
【０００９】[0009]
【化９】 ｎは０以上の数[Chemical 9] n is a number greater than or equal to 0
【００１０】上記アミン系硬化剤（Ｂ）としては、芳香
族アミンを用いることが好ましい。芳香族アミンとして
は、特に制限はなく、ＤＤＳ、ジアミノジフェニルメタ
ン、フェニレンジアミン、キシレンジアミン等が例示で
きる。特に、ＤＤＳは、耐熱性と硬化物物性のバランス
から好適に用いられる。本発明において、アミン系硬化
剤（Ｂ）の添加量は発明の骨格をなすものであり、アミ
ン系硬化剤（Ｂ）の添加量をエポキシ樹脂（Ａ）に対す
る化学量論量の１０質量％以上、７０質量％以下とし、
６０質量％以下とすることが好ましく、更に好ましくは
５０質量％以下である。また、下限については、１０質
量％以上添加しなければ、性能、特に耐熱性が低下して
しまう。２０質量％以上の添加がより望ましい。エポキ
シ樹脂／アミン硬化系においては、エポキシ樹脂のエポ
キシ基１個に対して、アミンの活性水素１個が反応する
ので、一般的にはエポキシ樹脂のエポキシ基とアミン系
硬化剤の活性水素の数を一致させるように配合したとき
に、最高の性能を発揮する。すなわち、配合するエポキ
シ樹脂のエポキシ当量と同当量の活性水素当量となるよ
うに、アミン系硬化剤の配合量を決定する。この配合量
が化学量論量である。An aromatic amine is preferably used as the amine-based curing agent (B). The aromatic amine is not particularly limited, and examples thereof include DDS, diaminodiphenylmethane, phenylenediamine, and xylenediamine. In particular, DDS is preferably used from the balance of heat resistance and physical properties of cured products. In the present invention, the addition amount of the amine-based curing agent (B) forms the skeleton of the invention, and the addition amount of the amine-based curing agent (B) is 10 mass% or more of the stoichiometric amount with respect to the epoxy resin (A). , 70% by mass or less,
The amount is preferably 60% by mass or less, and more preferably 50% by mass or less. Regarding the lower limit, unless added in an amount of 10% by mass or more, the performance, particularly the heat resistance will be deteriorated. It is more desirable to add 20% by mass or more. In an epoxy resin / amine curing system, one active hydrogen atom of an amine reacts with one epoxy group of an epoxy resin, so in general, the number of active hydrogen groups of an epoxy group of an epoxy resin and an amine curing agent is large. The best performance is obtained when blended to match. That is, the compounding amount of the amine-based curing agent is determined such that the active hydrogen equivalent is the same as the epoxy equivalent of the epoxy resin to be compounded. This blending amount is the stoichiometric amount.
【００１１】上記ルイス酸錯体（Ｃ）は、エポキシ樹脂
やアミンの反応性を高める触媒であり、三弗化硼素のア
ミン錯体が例示できる。上述したように、エポキシ樹脂
／アミン硬化系においては、通常１対１でエポキシ基と
活性水素が反応し、最高の性能を発揮するはずである
が、本発明者らは、耐熱性と機械物性、特に靱性や吸水
特性について検討した結果、既に公知であるアミン硬化
系のエポキシ樹脂組成物であっても、ルイス酸錯体系の
触媒が添加された系においては、アミン系硬化剤の添加
量を化学量論量より少なくしたときに、耐熱性と吸水性
のバランスに非常に優れることを見出したのである。こ
のように、ルイス酸錯体を用いて活性水素を不足する方
向にずらしたときに、耐熱性と吸水性のバランスが非常
に優れたエポキシ樹脂組成物となる現象について、その
機構は明らかではないが、ルイス酸錯体が関与している
のではないかと考えられる。ルイス酸錯体は、通常、エ
ポキシ樹脂とアミン系硬化剤の触媒として知られている
が、一方でエポキシ基同士のカチオン開環重合の触媒と
しても知られている。従って、不足した活性水素に対し
て、活性水素と反応しなかったエポキシ基は、ルイス酸
錯体によりエポキシ基同士で反応して架橋し、結果とし
て全エポキシ基は反応する。そのため、活性水素とエポ
キシ基の架橋以外に、エポキシ基の開環重合による架橋
がバランス良く含まれるために、本発明のエポキシ樹脂
組成物は、耐熱性と吸水性のバランスに非常に優れるも
のと推定する。The Lewis acid complex (C) is a catalyst that enhances the reactivity of epoxy resin and amine, and an example is an amine complex of boron trifluoride. As described above, in the epoxy resin / amine curing system, the epoxy group and the active hydrogen usually react in a one-to-one manner, and the best performance should be exhibited. However, the present inventors have found that heat resistance and mechanical properties are high. In particular, as a result of examining the toughness and water absorption characteristics, even in the already known amine-curing type epoxy resin composition, in the system in which the Lewis acid complex-type catalyst was added, the addition amount of the amine-type curing agent was changed. It has been found that when the amount is less than the stoichiometric amount, the balance between heat resistance and water absorption is extremely excellent. As described above, when the Lewis acid complex is used to shift the active hydrogen in the direction of being deficient, the mechanism of the epoxy resin composition having a very excellent balance between heat resistance and water absorption is not clear, but its mechanism is not clear. It is thought that the Lewis acid complex is involved. The Lewis acid complex is generally known as a catalyst for an epoxy resin and an amine-based curing agent, but is also known as a catalyst for cationic ring-opening polymerization of epoxy groups. Therefore, with respect to the insufficient active hydrogen, the epoxy groups that have not reacted with the active hydrogen react with each other by the Lewis acid complex and crosslink, and as a result, all the epoxy groups react. Therefore, in addition to the cross-linking of the active hydrogen and the epoxy group, since the cross-linking by ring-opening polymerization of the epoxy group is contained in a good balance, the epoxy resin composition of the present invention is very excellent in the balance of heat resistance and water absorption. presume.
【００１２】本発明のエポキシ樹脂組成物は、耐熱性や
吸水性、その他の物性を落とさずに、取り扱い性等を向
上させる目的で、必要に応じて、熱可塑性樹脂や無機物
粉体などの添加物を添加することができる。熱可塑性樹
脂としては、ポリエーテルスルホンやポリビニルホルマ
ールが好適に用いられ、無機物粉体としてはアエロジル
社製のアエロジルシリーズに代表されるシリカ系粉体が
好適に用いられる。尚、熱可塑性樹脂の添加方法として
は、微粒子状のものを分散して添加してもよいし、エポ
キシ樹脂に溶解して用いてもよい。The epoxy resin composition of the present invention may be added with a thermoplastic resin, an inorganic powder or the like, if necessary, for the purpose of improving the handling property and the like without deteriorating heat resistance, water absorption and other physical properties. Can be added. As the thermoplastic resin, polyether sulfone or polyvinyl formal is preferably used, and as the inorganic powder, silica-based powder represented by Aerosil series manufactured by Aerosil Co. is preferably used. As a method of adding the thermoplastic resin, fine particles may be dispersed and added, or may be dissolved in an epoxy resin and used.
【００１３】本発明のエポキシ樹脂組成物の用途として
は、特に限定はないが、繊維強化樹脂複合材料用のマト
リックス樹脂として、非常に好適に用いられる。補強材
としては、炭素繊維、ガラス繊維、ボロン繊維、スチー
ル繊維、アラミド繊維、ポリエチレン繊維等、有機、無
機のあらゆる繊維を使用できる。成形方法としても特に
制限はなく、プリプレグを経由する方法、フィラメント
ワインディングや引抜のような補強繊維に未硬化のエポ
キシ樹脂組成物を含浸させて硬化させる方法、ＲＴＭや
ハンドレイアップ、スプレーアップのようなクロス等に
エポキシ樹脂組成物を含浸させる方法等が例示できる。The use of the epoxy resin composition of the present invention is not particularly limited, but it is very suitably used as a matrix resin for a fiber-reinforced resin composite material. As the reinforcing material, carbon fiber, glass fiber, boron fiber, steel fiber, aramid fiber, polyethylene fiber, or any other organic or inorganic fiber can be used. There is no particular limitation on the molding method, such as a method of passing through a prepreg, a method of impregnating an uncured epoxy resin composition into a reinforcing fiber such as filament winding or drawing and curing, a method such as RTM, hand layup, and spray up. Examples of the method include impregnating a cloth or the like with an epoxy resin composition.
【００１４】[0014]
【実施例】以下、本発明のエポキシ樹脂組成物の具体的
な構成を実施例に基づいて、比較例と比較しながら説明
する。なお、実施例及び比較例のエポキシ樹脂組成物に
使用した各成分は、下記の略字で示す通りである。
Ｎ６７３：クレゾールノボラック型エポキシ樹脂「エピ
クロンＮ６７３」（大日本インキ化学工業社製）
ＨＰ７２００：構造式（i）に該当する固形状エポキシ
樹脂「エピクロンＨＰ７２００」（大日本インキ化学工
業社製）
Ｅｐ１０３２：構造式（ii）に該当する特殊ノボラック
型エポキシ樹脂「エピコート１０３２Ｓ５０」（ジャパ
ンエポキシレジン社製）
ＴＡＣＴＩＸ７４２：構造式（ii）に該当する特殊ノボ
ラック型エポキシ樹脂「ＴＡＣＴＩＸ７４２」（チバガ
イギー社製）
Ｅｐ１５７：構造式（iii）に該当する特殊ノボラック
型エポキシ樹脂「エピコート１５７Ｓ６５」（ジャパン
エポキシレジン社製）
Ｅｐ８２８：液状をなすビスフェノールＡ型エポキシ樹
脂「エピコート８２８」（ジャパンエポキシレジン社
製）
Ｅｐ６０４：ＴＧＤＤＭ「エピコート６０４」（ジャパ
ンエポキシレジン社製）
ＤＤＳ：ジアミノジフェニルスルホン「セイカキュア
Ｓ」（和歌山精化社製）
ＢＦ３：三弗化硼素モノエチルアミン錯体EXAMPLES Hereinafter, the concrete constitution of the epoxy resin composition of the present invention will be explained based on Examples while comparing with Comparative Examples. The components used in the epoxy resin compositions of Examples and Comparative Examples are as shown by the following abbreviations. N673: Cresol novolac type epoxy resin "Epiclon N673" (manufactured by Dainippon Ink and Chemicals, Inc.) HP7200: Solid epoxy resin "Epiclone HP7200" (manufactured by Dainippon Ink and Chemicals, Inc.) corresponding to structural formula (i) Ep1032: Structure Special novolac type epoxy resin corresponding to formula (ii) "Epicoat 1032S50" (manufactured by Japan Epoxy Resins Co., Ltd.) TACTIX 742: Special novolac type epoxy resin corresponding to formula (ii) "TACTIX 742" (manufactured by Ciba Geigy) Ep157: Structural formula Special novolac type epoxy resin “Epicoat 157S65” (manufactured by Japan Epoxy Resin Co., Ltd.) corresponding to (iii) Ep828: Bisphenol A type epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin Co.) in liquid form Ep60 : TGDDM "Epikote 604" (manufactured by Japan Epoxy Resins Co.) DDS: (manufactured by Wakayama Seikasha) diaminodiphenylsulfone "Seikakyua S" BF3: boron trifluoride monoethylamine complex
【００１５】（実施例１〜８）表１に示す組成を均一に
混合し、得られたエポキシ樹脂組成物を１８０℃、２時
間で成形した。尚、表中成分（Ｂ）のＤＤＳ添加量の
「％当量」は、エポキシ樹脂に対して化学量論量から算
出される当量の何％添加したかということであり、その
下段の「質量部」は、ＤＤＳの添加量を質量部に直した
ものである。(Examples 1 to 8) The compositions shown in Table 1 were uniformly mixed, and the resulting epoxy resin composition was molded at 180 ° C for 2 hours. The "% equivalent" of the DDS addition amount of the component (B) in the table is what percentage of the equivalent amount calculated from the stoichiometric amount with respect to the epoxy resin was added. "Is the amount of DDS added to be converted to parts by mass.
【００１６】[0016]
【表１】 [Table 1]
【００１７】（実施例９〜１２）表２に示す組成を均一
に混合し、得られたエポキシ樹脂組成物を１８０℃、２
時間で成形した。尚、表中成分（Ｂ）のＤＤＳ添加量の
「％当量」は、エポキシ樹脂に対して化学量論量から算
出される当量の何％添加したかということであり、その
下段の「質量部」は、ＤＤＳの添加量を質量部に直した
ものである。(Examples 9 to 12) The compositions shown in Table 2 were uniformly mixed, and the resulting epoxy resin compositions were mixed at 180 ° C and 2
Molded in time. The "% equivalent" of the DDS addition amount of the component (B) in the table is what percentage of the equivalent amount calculated from the stoichiometric amount with respect to the epoxy resin was added. "Is the amount of DDS added to be converted to parts by mass.
【００１８】[0018]
【表２】 [Table 2]
【００１９】（比較例１〜５）表３に示す組成を均一に
混合し、得られたエポキシ樹脂組成物を１８０℃、２時
間で成形した。尚、表中成分（Ｂ）のＤＤＳ添加量の
「％当量」は、エポキシ樹脂に対して化学量論量から算
出される当量の何％添加したかということであり、その
下段の「質量部」は、ＤＤＳの添加量を質量部に直した
ものである。Comparative Examples 1 to 5 The compositions shown in Table 3 were uniformly mixed, and the resulting epoxy resin composition was molded at 180 ° C. for 2 hours. The "% equivalent" of the DDS addition amount of the component (B) in the table is what percentage of the equivalent amount calculated from the stoichiometric amount with respect to the epoxy resin was added. "Is the amount of DDS added to be converted to parts by mass.
【００２０】[0020]
【表３】 [Table 3]
【００２１】〈評価方法〉実施例１〜１２及び比較例１
〜５で得られた硬化物を沸騰水中で２４時間浸漬し、吸
水させて下記の式に基づき吸水率を測定した。その結果
を表１〜３に示す。<Evaluation Method> Examples 1 to 12 and Comparative Example 1
The hardened | cured material obtained by -5 was immersed in boiling water for 24 hours, it was made to absorb water, and the water absorption rate was measured based on the following formula. The results are shown in Tables 1 to 3.
【数１】 [Equation 1]
【００２２】また、吸水前の硬化物の曲げ試験をＪＩＳ
Ｋ７１７１に準拠して実施した。また、吸水前と吸水
後の硬化物のガラス転移温度（Ｔｇ）を次の方法により
測定した。厚み２ｍｍ、幅１２ｍｍ、長さ６０ｍｍに切
り出したサンプルを用い、粘弾性測定装置（「ＲＤＡ−
７００」、レオメトリックス社製）を用いて測定した。
昇温条件は、室温付近から５℃／ステップで段階的に昇
温し、各温度で温度が安定してから、サンプル内部まで
温度を均一化させるために１分間保持した。その後サン
プルの動的せん断弾性率Ｇ'を測定した。得られたＧ'の
対数値を温度に対してプロットすると、図１のようなグ
ラフが得られる。このグラフ上において、硬化物がガラ
ス状態にある場合の傾きの接線ｌ１と、硬化物がガラス
状からゴム状へと転移している状態にある場合の傾きの
接線ｌ２との交点Ａの温度をＴｇとした。また、硬化物
の吸水前と吸水後のガラス転移温度の比を下記の式に基
づいて算出した。その結果を表１〜３に示す。In addition, the bending test of the cured product before water absorption is conducted according to JIS
It carried out based on K7171. The glass transition temperature (Tg) of the cured product before and after water absorption was measured by the following method. Using a sample cut into a thickness of 2 mm, a width of 12 mm and a length of 60 mm, a viscoelasticity measuring device (“RDA-
700 ", manufactured by Rheometrics).
As for the temperature raising conditions, the temperature was raised stepwise from around room temperature at 5 ° C./step, and after the temperature was stabilized at each temperature, it was held for 1 minute in order to make the temperature uniform inside the sample. After that, the dynamic shear modulus G ′ of the sample was measured. When the logarithmic value of the obtained G'is plotted against the temperature, a graph as shown in FIG. 1 is obtained. On this graph, the temperature at the intersection A of the tangent line l1 of the inclination when the cured product is in the glass state and the tangent line l2 of the inclination when the cured product is in the state of transition from glass to rubber is shown. It was Tg. Further, the ratio of the glass transition temperature before and after water absorption of the cured product was calculated based on the following formula. The results are shown in Tables 1 to 3.
【００２３】[0023]
【数２】 [Equation 2]
【００２４】表１、２から明らかなように、実施例１〜
１２で得られた硬化物は、優れた耐熱性を示し、吸水率
も低く、吸水後の耐熱性も高かった。特に、構造式（i
i）で表されるエポキシ樹脂の含有量がエポキシ樹脂
（Ａ）全体に対して５０質量％以上である実施例７、及
び実施例９〜１２で得られた硬化物は、吸水前後におい
て、非常に優れた耐熱性を示した。一方、比較例１〜５
で得られた硬化物は、耐熱性、吸水性のバランスが悪
く、特に吸水率が高いことが判明した。As is clear from Tables 1 and 2, Examples 1 to 1
The cured product obtained in No. 12 exhibited excellent heat resistance, low water absorption rate, and high heat resistance after water absorption. In particular, the structural formula (i
The cured products obtained in Example 7 and Examples 9 to 12 in which the content of the epoxy resin represented by i) is 50% by mass or more with respect to the entire epoxy resin (A) are extremely It showed excellent heat resistance. On the other hand, Comparative Examples 1-5
It was found that the cured product obtained in (1) had a poor balance of heat resistance and water absorption, and particularly high water absorption.
【００２５】[0025]
【発明の効果】以上説明したように、本発明のエポキシ
樹脂組成物によれば、耐熱性が良好であり、かつ吸水率
が低く、耐熱水性に優れた硬化物を得ることができる。
また、本発明のエポキシ樹脂組成物をマトリックス樹脂
として用いる繊維強化樹脂複合材料は工業用途等に非常
に有用である。As described above, according to the epoxy resin composition of the present invention, it is possible to obtain a cured product having good heat resistance, low water absorption and excellent hot water resistance.
Further, the fiber-reinforced resin composite material using the epoxy resin composition of the present invention as a matrix resin is very useful for industrial applications and the like.
【図１】 本発明の実施例で製造したエポキシ樹脂組成
物の温度に対する動的せん断弾性率Ｇ'をプロットした
グラフで、エポキシ樹脂組成物のガラス転移温度（Ｔ
ｇ）を示したものである。FIG. 1 is a graph in which a dynamic shear modulus G ′ of an epoxy resin composition produced in an example of the present invention is plotted with respect to a temperature, and a glass transition temperature (T
g) is shown.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F072 AA01 AA07 AD24 AD26 AD27 4J036 AC08 AF06 AF36 AJ08 DA05 DC10 DC19 JA11 ─────────────────────────────────────────────────── ─── Continued front page F term (reference) 4F072 AA01 AA07 AD24 AD26 AD27 4J036 AC08 AF06 AF36 AJ08 DA05 DC10 DC19 JA11
Claims (9)
（Ｂ）、ルイス酸錯体（Ｃ）を含有するエポキシ樹脂組
成物で、アミン系硬化剤（Ｂ）の添加量が、エポキシ樹
脂（Ａ）に対する化学量論量の１０質量％以上、７０質
量％以下であることを特徴とするエポキシ樹脂組成物。1. An epoxy resin composition containing an epoxy resin (A), an amine curing agent (B) and a Lewis acid complex (C), wherein the addition amount of the amine curing agent (B) is equal to that of the epoxy resin (A). 10% by mass or more and 70% by mass or less of the stoichiometric amount relative to
ノボラック型エポキシ樹脂、あるいは下記構造式で表さ
れるノボラック型のエポキシ樹脂のうち、少なくとも一
つを含むことを特徴とする請求項１記載のエポキシ樹脂
組成物。 【化１】 ｎは０以上の数 【化２】 ｎは０以上の数 【化３】 ｎは０以上の数2. The epoxy resin (A) contains at least one of a cresol novolac type epoxy resin and a novolac type epoxy resin represented by the following structural formula. Epoxy resin composition. [Chemical 1] n is a number of 0 or more. n is a number of 0 or more. n is a number greater than or equal to 0
族アミンを用いることを特徴とする請求項１記載のエポ
キシ樹脂組成物。3. The epoxy resin composition according to claim 1, wherein an aromatic amine is used as the amine curing agent (B).
ルスルホンであることを特徴とする請求項３記載のエポ
キシ樹脂組成物。4. The epoxy resin composition according to claim 3, wherein the aromatic amine is diaminodiphenyl sulfone.
のアミン錯体であることを特徴とする請求項１記載のエ
ポキシ樹脂組成物。5. The epoxy resin composition according to claim 1, wherein the Lewis acid complex (C) is an amine complex of boron trifluoride.
エポキシ樹脂（Ａ）に対する化学量論量の２０質量％以
上であることを特徴とする請求項１記載のエポキシ樹脂
組成物。6. The addition amount of the amine curing agent (B) is
20 mass% or more of a stoichiometric amount with respect to an epoxy resin (A), The epoxy resin composition of Claim 1 characterized by the above-mentioned.
エポキシ樹脂（Ａ）に対する化学量論量の６０質量％以
下であることを特徴とする請求項１記載のエポキシ樹脂
組成物。7. The addition amount of the amine curing agent (B) is
60 mass% or less of stoichiometric amount with respect to an epoxy resin (A), The epoxy resin composition of Claim 1 characterized by the above-mentioned.
ノボラック型のエポキシ樹脂を４０質量％以上含むこと
を特徴とする請求項２記載のエポキシ樹脂組成物。8. The epoxy resin (A) as a whole,
The epoxy resin composition according to claim 2, which contains 40% by mass or more of a novolac type epoxy resin.
のいずれかに記載のエポキシ樹脂組成物を用いることを
特徴とする繊維強化樹脂複合材料。9. The matrix resin as claimed in any one of claims 1 to 8.
A fiber-reinforced resin composite material, comprising the epoxy resin composition according to any one of 1.
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| JP2001123258 | 2001-04-20 | ||
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|---|---|---|---|---|
| JP2011132332A (en) * | 2009-12-24 | 2011-07-07 | Mitsubishi Rayon Co Ltd | Epoxy resin composition |
| CN103642003A (en) * | 2013-11-28 | 2014-03-19 | 江西洪都航空工业集团有限责任公司 | Prepreg curing process of epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011132332A (en) * | 2009-12-24 | 2011-07-07 | Mitsubishi Rayon Co Ltd | Epoxy resin composition |
| CN103642003A (en) * | 2013-11-28 | 2014-03-19 | 江西洪都航空工业集团有限责任公司 | Prepreg curing process of epoxy resin |
| US11066510B2 (en) | 2015-07-10 | 2021-07-20 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition, process for producing same, and uses of said composition |
| US11091627B2 (en) | 2017-01-10 | 2021-08-17 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition |
| US11111382B2 (en) | 2017-01-10 | 2021-09-07 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition |
| US11292872B2 (en) | 2017-01-10 | 2022-04-05 | Sumitomo Seika Chemicals Co., Ltd. | Epoxy resin composition |
| US11603466B2 (en) | 2017-01-10 | 2023-03-14 | Sumitomo Seika Chemicals Co.. Ltd. | Epoxy resin composition |
| JP2020158727A (en) * | 2019-03-28 | 2020-10-01 | 味の素株式会社 | Epoxy resin composition |
| JP7166525B2 (en) | 2019-03-28 | 2022-11-08 | 味の素株式会社 | epoxy resin composition |
| CN114989398A (en) * | 2022-05-16 | 2022-09-02 | 中国电子科技集团公司第三十八研究所 | Solvent-free RTM resin body for ultralow temperature and wide temperature environment and preparation method thereof |
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