JP2005060481A - Heat resistant epoxy hardener - Google Patents

Heat resistant epoxy hardener Download PDF

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JP2005060481A
JP2005060481A JP2003290635A JP2003290635A JP2005060481A JP 2005060481 A JP2005060481 A JP 2005060481A JP 2003290635 A JP2003290635 A JP 2003290635A JP 2003290635 A JP2003290635 A JP 2003290635A JP 2005060481 A JP2005060481 A JP 2005060481A
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epoxy resin
molecular weight
heat
resistant epoxy
curing agent
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Fumihiko Akutsu
文彦 阿久津
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Chiba University NUC
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Chiba University NUC
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a hardened epoxy resin having high heat resistance. <P>SOLUTION: The heat resistant hardened epoxy resin is obtained by hardening an epoxy resin with polyaminophenyl quinoxaline as the hardener and has an actual mol.wt. between crosslinking points 1.0-3.0 times the theoretical mol.wt. between crosslinking points. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明は、耐熱性エポキシ硬化剤に関する。   The present invention relates to a heat-resistant epoxy curing agent.

エポキシ樹脂は接着性、接着強度、非収縮性、電気特性などに優れているため、種々の用途で広く利用されている。   Epoxy resins are widely used in various applications because they are excellent in adhesiveness, adhesive strength, non-shrinkage, electrical properties, and the like.

一般的に、エポキシ樹脂の耐熱構成を向上させるためには、硬化剤の構造中に芳香環を導入すれば効果があることがわかっている。従来、汎用エポキシ樹脂の耐熱性硬化剤としては、４，４’−ジアミノジフェニルスルホン（ＤＤＳ）や、４，４’−ジアミノジフェニルメタン（ＤＤＭ）が知られている（たとえば特許文献１参照）。これらの硬化剤を用いて製造されたエポキシ樹脂硬化物は室温では十分な接着強度を示す。しかし、従来のエポキシ樹脂硬化物を高温にさらすと、その接着強度は１２０℃付近から急速に低下し、１８０℃においてはＤＤＭ硬化の場合で室温の６７％、ＤＤＳ硬化の場合で室温の５４％にまで低下する。このように従来のエポキシ樹脂硬化物では耐熱性が十分でないという問題があった。
特開平７−２５８３８９号公報 In general, it has been found that introducing an aromatic ring into the structure of the curing agent is effective for improving the heat-resistant structure of the epoxy resin. Conventionally, 4,4′-diaminodiphenylsulfone (DDS) and 4,4′-diaminodiphenylmethane (DDM) are known as heat-resistant curing agents for general-purpose epoxy resins (see, for example, Patent Document 1). Epoxy resin cured products produced using these curing agents exhibit sufficient adhesive strength at room temperature. However, when the conventional epoxy resin cured product is exposed to a high temperature, its adhesive strength rapidly decreases from around 120 ° C., and at 180 ° C., 67% of the room temperature in the case of DDM curing and 54% of the room temperature in the case of DDS curing. Drop to. Thus, the conventional epoxy resin cured product has a problem that heat resistance is not sufficient.
JP 7-258389 A

本発明の目的は、高い耐熱性を示す硬化物を与える耐熱性エポキシ硬化剤を提供することにある。   An object of the present invention is to provide a heat-resistant epoxy curing agent that gives a cured product exhibiting high heat resistance.

本発明に係る耐熱性エポキシ樹脂硬化剤は、キノキサリン環を有するポリアミンであって、アミノ基としてｐ−またはｍ−アミノフェニル基を有する。   The heat-resistant epoxy resin curing agent according to the present invention is a polyamine having a quinoxaline ring, and has a p- or m-aminophenyl group as an amino group.

本発明に係る耐熱性エポキシ樹脂硬化物は、エポキシ樹脂と、硬化剤であるポリアミノフェニルキノキサリンとを硬化させたエポキシ樹脂硬化物であって、架橋点間分子量が理論的架橋点間分子量の１．０〜３．０倍であることを特徴とする。   The heat-resistant epoxy resin cured product according to the present invention is an epoxy resin cured product obtained by curing an epoxy resin and polyaminophenylquinoxaline as a curing agent, and the molecular weight between crosslink points is 1. It is 0 to 3.0 times.

本発明の耐熱性エポキシ硬化剤は複素環を含み、しかも１，２−置換構造を有するポリアミノフェニルキノキサリンである場合には、架橋度が高く、架橋点間分子量が理論的架橋点間分子量の１．０〜３．０倍であるエポキシ樹脂硬化物が得られ、高い耐熱性を達成することができる。   When the heat-resistant epoxy curing agent of the present invention is a polyaminophenylquinoxaline containing a heterocyclic ring and having a 1,2-substituted structure, the degree of crosslinking is high, and the molecular weight between crosslinking points is 1 of the molecular weight between theoretical crosslinking points. An epoxy resin cured product of 0.0 to 3.0 times is obtained, and high heat resistance can be achieved.

以下、本発明を実施例に基づいて説明する。
エポキシ樹脂として旭電化製ＥＰ−４１００（ビスフェノールＡのジグリシジルエーテル）を用意した。また、硬化剤として、下記の４種のものを用意した。
ｐ−ＢＡＰＱ：２，３−ビス（ｐ−アミノフェニル）キノキサリン
ｍ−ＢＡＰＱ：２，３−ビス（ｍ−アミノフェニル）キノキサリン
ＤＤＳ：４，４’−ジアミノジフェニルスルホン
ＤＤＭ：４，４’−ジアミノジフェニルメタン
これらの硬化剤の化学式を下記に示す。

Figure 2005060481
Hereinafter, the present invention will be described based on examples.
As an epoxy resin, Asahi Denka EP-4100 (bisphenol A diglycidyl ether) was prepared. In addition, the following four types of curing agents were prepared.
p-BAPQ: 2,3-bis (p-aminophenyl) quinoxaline m-BAPQ: 2,3-bis (m-aminophenyl) quinoxaline DDS: 4,4′-diaminodiphenylsulfone DDM: 4,4′-diamino Diphenylmethane The chemical formula of these curing agents is shown below.
Figure 2005060481

上記のエポキシ樹脂と各々の硬化剤を、エポキシ基とアミノ基が当量（モル比２：１）になるように混合し、加熱硬化してエポキシ樹脂硬化物を得た。
それぞれのエポキシ樹脂硬化物の熱変形温度および架橋点間分子量比を求めた。
熱変形温度は、ＪＩＳ Ｋ−７１９６に従い、針入法によるＴＭＡ(thermal mechanical analysis)を行うことによって測定した。
架橋点間分子量比は、［架橋点間分子量（Ｍｃ）］／［理論的架橋点間分子量］の比率である。架橋点間分子量（Ｍｃ）は理想ゴム弾性理論に基づいて求められる。ここで、架橋点間分子量（Ｍｃ）が理論的架橋点間分子量より小さくなることはないので、架橋点間分子量比は１．０以上である。一方、架橋点間分子量比が３．０を超えると、十分な耐熱性が得られない。 Said epoxy resin and each hardening | curing agent were mixed so that an epoxy group and an amino group might become equivalent (molar ratio 2: 1), and it heat-hardened and obtained the epoxy resin hardened | cured material.
The thermal deformation temperature and the molecular weight ratio between crosslink points of each cured epoxy resin were determined.
The thermal deformation temperature was measured by performing TMA (thermal mechanical analysis) by a penetration method according to JIS K-7196.
The molecular weight ratio between crosslinking points is the ratio of [molecular weight between crosslinking points (Mc)] / [theoretical molecular weight between crosslinking points]. The molecular weight (Mc) between crosslinking points is determined based on the ideal rubber elasticity theory. Here, the molecular weight between cross-linking points (Mc) is never smaller than the theoretical molecular weight between cross-linking points, so the molecular weight ratio between cross-linking points is 1.0 or more. On the other hand, when the molecular weight ratio between cross-linking points exceeds 3.0, sufficient heat resistance cannot be obtained.

また、上記のエポキシ樹脂と各々の硬化剤を、エポキシ基とアミノ基とが等量になるように混合し、ステンレススチール試験片に塗布した後、もう１枚のステンレススチール試験片を圧着して加熱することにより接着した。これらの試料について引張試験を行うことにより、接着強度を測定した。
これらの結果を表１に示す。

Figure 2005060481
Also, after mixing the above epoxy resin and each curing agent so that the epoxy groups and amino groups are in equal amounts, and applying them to the stainless steel test piece, the other stainless steel test piece is crimped. Bonded by heating. The adhesive strength was measured by performing a tensile test on these samples.
These results are shown in Table 1.
Figure 2005060481

表１から、実施例のエポキシ樹脂硬化物は、架橋点間分子量比が３以下である点で比較例（従来技術）と異なり、比較例に比べて熱変形温度が高く高温における接着強度が改善されていることがわかる。本発明のエポキシ樹脂硬化物では、硬化剤として、複素環を含み、かつ１，２−置換構造を有するｐ−ＢＡＰＱまたはｍ−ＢＡＰＱを用いて架橋度を上げたことによって、上記のような高い耐熱性が得られた。   From Table 1, the cured epoxy resin of the examples is different from the comparative example (conventional technology) in that the molecular weight ratio between crosslinking points is 3 or less, and has a higher heat deformation temperature and improved adhesive strength at high temperatures compared to the comparative example. You can see that In the cured epoxy resin of the present invention, the degree of crosslinking is increased by using p-BAPQ or m-BAPQ containing a heterocyclic ring and having a 1,2-substituted structure as a curing agent. Heat resistance was obtained.

本発明のエポキシ樹脂硬化物は、他の特性を維持しつつ、耐熱性が改善されているので、さらに利用分野が広がることが期待される。   The cured epoxy resin product of the present invention has improved heat resistance while maintaining other properties, and thus is expected to further expand the field of application.

Claims (3)

キノキサリン環を有するポリアミンであって、アミノ基としてｐ−またはｍ−アミノフェニル基を有することを特徴とする耐熱性エポキシ樹脂硬化剤。   A heat-resistant epoxy resin curing agent, which is a polyamine having a quinoxaline ring and having a p- or m-aminophenyl group as an amino group. エポキシ樹脂と、硬化剤であるポリアミノフェニルキノキサリンとを硬化させたエポキシ樹脂硬化物であって、架橋点間分子量が理論的架橋点間分子量の１．０〜３．０倍であることを特徴とする耐熱性エポキシ樹脂硬化物。   A cured epoxy resin obtained by curing an epoxy resin and polyaminophenylquinoxaline as a curing agent, characterized in that the molecular weight between crosslink points is 1.0 to 3.0 times the molecular weight between theoretical crosslink points. Heat-resistant epoxy resin cured product. 前記ポリアミノフェニルキノキサリンが、２，３−ビス（ｐ−アミノフェニル）キノキサリンまたは２，３−ビス（ｍ−アミノフェニル）キノキサリンであることを特徴とする請求項２に記載の耐熱性エポキシ樹脂硬化物。   3. The heat-resistant epoxy resin cured product according to claim 2, wherein the polyaminophenylquinoxaline is 2,3-bis (p-aminophenyl) quinoxaline or 2,3-bis (m-aminophenyl) quinoxaline. .
JP2003290635A 2003-08-08 2003-08-08 Heat resistant epoxy hardener Pending JP2005060481A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298788A (en) * 2004-04-15 2005-10-27 Chiba Univ Heat-resistant and high strength epoxy resin
JP2005314624A (en) * 2004-04-28 2005-11-10 Chiba Univ High-strength epoxy resin
JP2010059059A (en) * 2008-09-01 2010-03-18 Asahi Kasei E-Materials Corp Compound comprising quinoxaline skeleton, and method of producing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298788A (en) * 2004-04-15 2005-10-27 Chiba Univ Heat-resistant and high strength epoxy resin
JP2005314624A (en) * 2004-04-28 2005-11-10 Chiba Univ High-strength epoxy resin
JP2010059059A (en) * 2008-09-01 2010-03-18 Asahi Kasei E-Materials Corp Compound comprising quinoxaline skeleton, and method of producing the same

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