JP2004018711A - Method for adjusting pot life of epoxy resin composition - Google Patents
Method for adjusting pot life of epoxy resin composition Download PDFInfo
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Abstract
【課題】エポキシ樹脂組成物の常温硬化におけるポットライフの調節方法を提供する。
【解決手段】安全衛生上優位であり、保存安定性が良好である特定構造のポリアミノ化合物とスチレンとの付加反応により得られる特定構造のポリアミノ化合物を含むポリアミノ組成物を必須成分とするエポキシ樹脂硬化剤を用いる
【選択図】 無An object of the present invention is to provide a method for adjusting a pot life in room temperature curing of an epoxy resin composition.
An epoxy resin cured with a polyamino composition containing a polyamino compound having a specific structure obtained by an addition reaction of a polyamino compound having a specific structure and styrene, which is superior in safety and health and has good storage stability, as an essential component [Selection diagram]
Description
【０００１】
【発明の属する技術分野】
本発明は特定のポリアミノ組成物をエポキシ樹脂硬化剤の必須成分として、他の成分と混合して用いることを特徴とするエポキシ樹脂組成物のポットライフ調節方法に関する。
【０００２】
【従来の技術】
各種ポリアミノ化合物がエポキシ樹脂硬化剤およびその原料として用いられていることは広く知られている。これらのエポキシ樹脂硬化剤を利用した常温硬化用エポキシ樹脂組成物は、特に船舶・橋梁・陸海上鉄構築物用防食塗料などの塗料分野、コンクリート構造物のライニング・補強・補修、建築物の床材、上下水道設備のライニング、舗装材、接着材などの土木・建築分野に広く利用されている。中でも後述する（１）式で示されるポリアミノ化合物およびこれを原料とするエポキシ樹脂硬化剤は他のポリアミノ化合物およびこれを原料とするエポキシ樹脂硬化剤と比較して、エポキシ樹脂組成物に良好な硬化性を与える、光沢、平滑性に優れたエポキシ樹脂硬化塗膜を与える、耐水性、耐薬品性に優れたエポキシ樹脂硬化物を与える等の特長を有している。
【０００３】
しかし、その反面（１）式で示されるポリアミノ化合物およびこれらを原料とするエポキシ樹脂硬化剤はエポキシ樹脂との反応性が高いために、そのエポキシ樹脂組成物は常温硬化ではポットライフが短く、作業性が悪いという欠点を有している。
【０００４】
従来からポリアミノ化合物とアクリロニトリルとのマイケル付加反応により得られるシノエチル化ポリアミノ化合物をエポキシ樹脂硬化剤として使用した場合にエポキシ樹脂組成物に長いポットライフを与えることが知られており（例えば、垣内弘編著、新エポキシ樹脂、１８６頁、昭晃堂、（１９８５））、（１）式で示されるポリアミノ化合物およびこれらを原料とするエポキシ樹脂硬化剤に混合し、ポットライフを調節することできる。しかし、アクリロニトリルは特定化学物質および劇物に指定されているため、近年では安全衛生上から該ポリアミノ化合物をエポキシ樹脂硬化剤に混合して使用することは少なくなってきている。
【０００５】
また、特開平１１−８０３２２号はポリアミノ化合物と不飽和カルボン酸エステル化合物とのマイケル付加反応による得られる、低粘度で、有害性が低い化合物に関するものであり、該化合物をエポキシ樹脂硬化剤として使用したエポキシ樹脂組成物の常温硬化におけるポットライフ延長方法が開示されているが、該化合物中にアミノ基とエステル基が存在するために、保存中にエステルアミド交換反応が進行し、アミドの生成により粘度上昇が生じ保存安定性が悪く、また、エステル基が減少するためにエポキシ樹脂硬化剤として使用した場合にエポキシ樹脂組成物のポットライフ調節効果は小さくなる。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、エポキシ樹脂硬化剤の必須成分として、安全衛生上優位であり、保存安定性が良好である特定構造のポリアミノ化合物を含むポリアミノ組成物を他のポリアミノ化合物成分と混合して使用し、エポキシ樹脂組成物の常温硬化におけるポットライフの調節方法を提供することにある。
【０００７】
【発明が解決するための手段】
本発明者らは、鋭意検討した結果、安全衛生上優位であり、保存安定性が良好である（１）式で示されるポリアミノ化合物とスチレンとの付加反応により得られ、（２）式で示される互いに側鎖基の構成が異なる各付加物からなるポリアミノ化合物を必須成分とするポリアミノ組成物を他のポリアミノ化合物成分と混合して使用することでエポキシ樹脂組成物常温硬化におけるポットライフを調節できることを見出し、本発明に至った。
【０００８】
即ち本発明は、（１）式で示されるポリアミノ化合物Ａとスチレンとの付加反応により得られ、（２）式で示される互いに側鎖基の構成が異なる各付加物から選ばれる少なくとも１つであるポリアミノ化合物Ｂを必須成分とするポリアミノ組成物を含むエポキシ樹脂硬化剤を用いることを特徴とするエポキシ樹脂組成物のポットライフ調節方法を提供する。
【化３】
【発明の実施の形態】
本発明で使用される（１）式で示されるポリアミノ化合物Ａとしては、オルソキシレンジアミン、メタキシリレンジアミン、パラキシリレンジアミン、１，２−ビス（アミノメチル）シクロヘキサン、１，３−ビス（アミノメチル）シクロヘキサン、１，４−ビス（アミノメチル）シクロヘキサンなどがあげられる。この中で特に好ましいのは、メタキシリレンジアミン、１，３−ビス（アミノメチル）シクロヘキサンである。
【００１０】
本発明で使用されるアミノ化合物Ｂとは、前記アミノ化合物Ａとスチレンとの付加反応により得られ、（２）式で示される互いに側鎖基の構成が異なる各付加物から選ばれる少なくとも１つの化合物からなる。ここで、互いに側鎖基の構成が異なる各付加物とは、（２）式において、Ｒ１、Ｒ２およびＲ３のいずれもが水素である付加物、いずれか２つが水素であり、残り１つがフェネチル基である付加物、いずれか２つがフェネチル基であり、残り１つが水素である付加物、およびいずれもがフェネチル基である付加物である。本発明では、これらの付加物は単独あるいは混合物として用いられる。
【００１１】
本発明において、アミノ化合物Ｂを製造する際には、強塩基性を呈する触媒を使用することが好ましい。例えば、アルカリ金属、アルカリ金属アミド、アルキル化アルカリ金属などがあるが、好ましくはアルカリ金属アミド（一般式ＭＮＲＲ’：Ｍはアルカリ金属、Ｎは窒素、ＲおよびＲ’は各々独立して水素またはアルキル基である）であり、特にリチウムアミド（ＬｉＮＨ２）が好ましい。
【００１２】
本発明において、ポリアミノ組成物とは、前記ポリアミド化合物Ｂを必須成分として含むものであり、ポリアミド化合物Ｂ以外のポリアミノ化合物成分は、脂肪族ポリアミノ化合物、脂環族ポリアミノ化合物、芳香族ポリアミノ化合物、およびこれらを原料とする変性ポリアミノ化合物から選ばれる。これらのポリアミノ化合物の中で（１）式で示されるポリアミノ化合物のＡがフェニレン基である脂肪族ポリアミノ化合物の変性ポリアミノ化合物、あるいは（１）式で示されるポリアミノ化合物のＡがシクロヘキシレン基である脂環族ポリアミノ化合物の変性ポリアミノ化合物が好ましい。
【００１３】
前記変性ポリアミノ化合物は、原料であるポリアミノ化合物を、フェノール系化合物とアルデヒド化合物とのマンニッヒ反応による変性、エポキシ化合物との反応による変性、カルボキシル基を有する化合物との反応による変性、およびアクリル系化合物とのマイケル反応による変性から選ばれる少なくとも１つの方法で変性して得られる。
【００１４】
前記ポリアミノ化合物Ｂと他のポリアミノ化合物成分との混合割合は任意に選ばれ、特に限定されるものではないが、ポリアミノ化合物Ｂの混合割合が多いほどエポキシ樹脂組成物のポットライフは長くなる。従って、この混合割合を適切に選定することにより、目的に適したポットライフを有するエポキシ樹脂組成物が得られる。
【００１５】
【実施例】
以下に、本発明を実施例により具体的に説明するが、本発明はこれらの実施例により限定されるものではない。
【００１６】
合成例１
撹拌装置、温度計、窒素導入管、滴下漏斗、冷却管を備えた２リットルフラスコに、メタキシリレンジアミン（三菱ガス化学（株）製、以下ＭＸＤＡと記す）８１７．２ｇ（６．０モル）とリチウムアミド（Ｍｅｒｋ社製試薬）２．９ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン（和光純薬（株）製、試薬特級）６２５．２ｇ（６．０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。
その後室温に冷却し、仕込んだリチウムアミドの１０倍モル量の水２３．４ｇ（１．３モル）を加え撹拌した。フラスコ内液中の沈殿物をろ過で分離後、減圧蒸留で水を留去し、ポリアミノ組成物Ａ１３８０．７ｇを得た。
【００１７】
合成例２
実施例１と同様のフラスコにＭＸＤＡ６８１．０ｇ（５．０モル）とリチウムアミド３．７ｇ（０．１６モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながらスチレン７８１．５ｇ（７．５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後室温に冷却し、仕込んだリチウムアミドの１０倍モル量の水２８．８ｇ（１．６モル）を加え、合成例１と同様の操作を行い、ポリアミノ組成物Ｂ１３９５．６ｇを得た。
【００１８】
合成例３
合成例１と同様のフラスコに、１，３−ビス（アミノメチル）シクロヘキサン（三菱ガス化学（株）製、以下１，３−ＢＡＣと記す）８５３．２ｇ（６．０モル）とリチウムアミド３．０ｇ（０．１３モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながら、スチレン６２５．２ｇ（６．０モル）を２時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後室温に冷却し、仕込んだリチウムアミドの１０倍モル量の水２３．４ｇ（１．３モル）を加え、合成例１と同様の操作を行い、ポリアミノ組成物Ｃ１４０９．３ｇを得た。
【００１９】
合成例４
合成例１と同様のフラスコに１，３−ＢＡＣ７１１．０ｇ（５．０モル）とリチウムアミド３．７ｇ（０．１６モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃に保ちながらスチレン７８１．５ｇ（７．５モル）を２．５時間かけて滴下した。滴下終了後、８０℃で１時間保った。その後室温に冷却し、仕込んだリチウムアミドの１０倍モル量の水２８．８ｇ（１．６モル）を加え、合成例１と同様の操作を行い、ポリアミノ組成物Ｄ１４２４．４ｇを得た。
【００２０】
合成例５
実施例１と同様のフラスコに、ＭＸＤＡ６１２．９ｇ（４．５モル）とフェノール４２３．４５ｇ（４．５モル）を仕込み、窒素気流下、撹拌しながら８０℃に昇温した。８０℃でホルマリン（８％メタノール含有３７％水溶液）２４３．３ｇ（３．０モル）を１．５時間かけて滴下した。滴下終了後、１００℃に昇温し１．５時間反応を行った。その後水を留去しながら２時間かけて１５０℃まで昇温し、同温度で１時間反応を行い、マンニッヒ反応による変性ポリアミノ化合物Ｅ１０７２．０ｇを得た。
【００２１】
合成例６
合成例５のＭＸＤＡを１，３−ＢＡＣ６３９．９ｇ（４．５モル）に変え、同様の方法で合成を行い、変性ポリアミノ化合物Ｆ１０９５．６ｇを得た。
【００２２】
合成例７〜９
合成例１で示したポリアミノ組成物Ａと合成例５で示した変性ポリアミノ化合物Ｅを表１に示す割合で混合し、エポキシ樹脂硬化剤Ｇ〜Ｉを得た。
【００２３】
合成例１０〜１２
合成例２で示したポリアミノ組成物Ｂと合成例５で示した変性ポリアミノ化合物Ｅを表１に示す割合で混合し、エポキシ樹脂硬化剤Ｊ〜Ｌを得た。
【００２４】
合成例１３〜１５
合成例３で示したポリアミノ組成物Ｃと合成例６で示した変性ポリアミノ化合物Ｆを表２に示す割合で混合し、エポキシ樹脂硬化剤Ｍ〜Ｏを得た。
【００２５】
合成例１６〜１８
合成例４で示したポリアミノ組成物Ｄと合成例６で示した変性ポリアミノ化合物Ｅを表２に示す割合で混合し、エポキシ樹脂硬化剤Ｐ〜Ｒを得た。
【００２６】
実施例１〜４
合成例１〜４で得られたポリアミノ組成物Ａ〜Ｄの保存安定性を評価した。評価結果を表３に示した。
【００２７】
実施例５〜１０
合成例７〜９で示したエポキシ樹脂硬化剤Ｇ〜Ｉおよび合成例１０〜１２で示したエポキシ樹脂硬化剤Ｊ〜ＬをビスフェノールＡ型液状エポキシ樹脂（商品名：エピコート８２８、ジャパンエポキシレジン（株）製）と表２に示す割合で配合しエポキシ樹脂組成物を調製した。得られたエポキシ樹脂組成物のポットライフを測定した。測定結果を表４に示した。
【００２８】
実施例１１〜１６
合成例１３〜１５で示したエポキシ樹脂硬化剤Ｍ〜Ｏおよび合成例１６〜１８で示したエポキシ樹脂硬化剤Ｐ〜ＲをビスフェノールＡ型液状エポキシ樹脂（商品名：エピコート８２８、ジャパンエポキシレジン（株）製）と表２に示す割合で配合しエポキシ樹脂組成物を調製した。得られたエポキシ樹脂組成物のポットライフを測定した。測定結果を表５に示した。
【００２９】
【表１】
【表２】
【表３】
【表４】
【表５】
ポリアミノ組成物およびエポキシ樹脂組成物の評価は以下の方法で行った。
〈保存安定性〉
ポリアミノ組成物２００ｇを２２５ｍｌのガラス瓶に入れて密封し、２３℃、５０％ＲＨの条件下に１ヶ月間保存後、外観変化および粘度変化を観察した。
〈ポットライフ〉
エポキシ樹脂組成物１００ｇを３００ｍｌのポリプロピレン製カップに入れ、２３℃、５０％ＲＨの条件下に放置し、最高発熱温度への到達時間を測定した。
【００３５】
【発明の効果】
以上の実施例から明らかなように、安全衛生上優位であり、保存安定性が良好である（１）式で示されるポリアミノ化合物とスチレンとの付加反応により得られ、（２）式で示される互いに側鎖基の異なる各付加物から構成されるポリアミノ化合物を必須成分として、他のポリアミノ化合物成分と混合して使用することでエポキシ樹脂組成物のポットライフを調節することができる。これにより、目的に応じて適切なポットライフを有するエポキシ樹脂組成物を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for adjusting the pot life of an epoxy resin composition, wherein a specific polyamino composition is used as an essential component of an epoxy resin curing agent and mixed with other components.
[0002]
[Prior art]
It is widely known that various polyamino compounds are used as epoxy resin curing agents and their raw materials. Room temperature curing epoxy resin compositions using these epoxy resin curing agents are particularly useful in the field of paints such as anticorrosive paints for ships, bridges, and onshore and shore iron structures, lining, reinforcing and repairing concrete structures, and flooring materials for buildings. It is widely used in civil engineering and construction fields such as lining of water and sewage equipment, paving materials, and adhesives. Above all, the polyamino compound represented by the formula (1) described below and the epoxy resin curing agent using the same as a raw material are better cured for the epoxy resin composition than other polyamino compounds and the epoxy resin curing agent using the same as the raw material. It has features such as giving an epoxy resin cured coating film having excellent gloss and smoothness, and giving a cured epoxy resin material having excellent water resistance and chemical resistance.
[0003]
However, on the other hand, the polyamino compound represented by the formula (1) and the epoxy resin curing agent using these as a raw material have high reactivity with the epoxy resin. It has the drawback of poor properties.
[0004]
It has been known that when a sinoethylated polyamino compound obtained by a Michael addition reaction between a polyamino compound and acrylonitrile is used as an epoxy resin curing agent, an epoxy resin composition has a long pot life (for example, edited by Hiroshi Kakiuchi) New epoxy resin, page 186, Shokodo, (1985)), a polyamino compound represented by the formula (1) and an epoxy resin curing agent using these as a raw material to control the pot life. However, since acrylonitrile is specified as a specific chemical substance and a deleterious substance, the use of the polyamino compound mixed with an epoxy resin curing agent has been reduced in recent years from the viewpoint of safety and health.
[0005]
JP-A-11-80322 relates to a low-viscosity, low-harmful compound obtained by the Michael addition reaction of a polyamino compound and an unsaturated carboxylic acid ester compound, and the compound is used as an epoxy resin curing agent. A method for extending the pot life in the room temperature curing of the epoxy resin composition has been disclosed.However, due to the presence of an amino group and an ester group in the compound, an ester amide exchange reaction proceeds during storage, and amide formation is caused. When the epoxy resin composition is used as a curing agent for an epoxy resin, the effect of adjusting the pot life of the epoxy resin composition is reduced when the viscosity is increased and the storage stability is poor.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to use a polyamino composition containing a polyamino compound having a specific structure which is superior in safety and hygiene and has good storage stability as an essential component of an epoxy resin curing agent by mixing with another polyamino compound component. It is another object of the present invention to provide a method for adjusting a pot life in curing an epoxy resin composition at room temperature.
[0007]
Means for Solving the Invention
The present inventors have conducted intensive studies and as a result, obtained by the addition reaction of a polyamino compound represented by formula (1) with styrene, which is superior in safety and health and has good storage stability, and which is represented by formula (2) The pot life in the room temperature curing of the epoxy resin composition can be adjusted by using a polyamino compound containing a polyamino compound composed of each adduct having a different side chain group as an essential component in combination with other polyamino compound components. And found the present invention.
[0008]
That is, the present invention provides at least one selected from the adducts obtained by the addition reaction of the polyamino compound A represented by the formula (1) with styrene and having different side chain groups represented by the formula (2). Provided is a method for adjusting the pot life of an epoxy resin composition, characterized by using an epoxy resin curing agent containing a polyamino composition containing a certain polyamino compound B as an essential component.
Embedded image
BEST MODE FOR CARRYING OUT THE INVENTION
Examples of the polyamino compound A represented by the formula (1) used in the present invention include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-bis (aminomethyl) cyclohexane, and 1,3-bis ( Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like. Of these, meta-xylylenediamine and 1,3-bis (aminomethyl) cyclohexane are particularly preferred.
[0010]
The amino compound B used in the present invention is obtained by an addition reaction between the amino compound A and styrene, and is at least one selected from adducts having different side chain groups represented by the formula (2). Consists of a compound. Here, each of the adducts having a different side chain group structure is an adduct in which all of R1, R2 and R3 are hydrogen in formula (2), any two of which are hydrogen, and the other one is phenethyl Adducts which are groups, any two of which are phenethyl groups, and the other one is hydrogen, and all of which are phenethyl groups. In the present invention, these adducts are used alone or as a mixture.
[0011]
In the present invention, when producing the amino compound B, it is preferable to use a catalyst exhibiting strong basicity. For example, there are alkali metals, alkali metal amides, alkylated alkali metals, etc., and preferably alkali metal amides (general formula NMRR ′: M is an alkali metal, N is nitrogen, R and R ′ are each independently hydrogen or alkyl) And lithium amide (LiNH 2 ) is particularly preferred.
[0012]
In the present invention, the polyamino composition includes the polyamide compound B as an essential component, and the polyamino compound component other than the polyamide compound B includes an aliphatic polyamino compound, an alicyclic polyamino compound, an aromatic polyamino compound, and These are selected from modified polyamino compounds using these as raw materials. Among these polyamino compounds, a modified polyamino compound of an aliphatic polyamino compound in which A of the polyamino compound represented by the formula (1) is a phenylene group, or A of a polyamino compound represented by the formula (1) is a cyclohexylene group Modified polyamino compounds of alicyclic polyamino compounds are preferred.
[0013]
The modified polyamino compound is a raw material polyamino compound, modified by a Mannich reaction between a phenolic compound and an aldehyde compound, modified by a reaction with an epoxy compound, modified by a reaction with a compound having a carboxyl group, and an acrylic compound. And denatured by at least one method selected from the Michael reaction.
[0014]
The mixing ratio between the polyamino compound B and the other polyamino compound components is arbitrarily selected and is not particularly limited. However, the pot life of the epoxy resin composition becomes longer as the mixing ratio of the polyamino compound B increases. Therefore, by properly selecting the mixing ratio, an epoxy resin composition having a pot life suitable for the purpose can be obtained.
[0015]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
[0016]
Synthesis Example 1
817.2 g (6.0 mol) of meta-xylylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd .; hereinafter, referred to as MXDA) in a 2 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and cooling tube. And 2.9 g (0.13 mol) of lithium amide (a reagent manufactured by Merk) were charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 1 hour.
Thereafter, the mixture was cooled to room temperature, 23.4 g (1.3 mol) of water having a molar amount 10 times that of the charged lithium amide was added, and the mixture was stirred. After the precipitate in the flask was separated by filtration, water was distilled off under reduced pressure to obtain 1380.7 g of a polyamino composition A.
[0017]
Synthesis Example 2
The same flask as in Example 1 was charged with 681.0 g (5.0 mol) of MXDA and 3.7 g (0.16 mol) of lithium amide, and heated to 80 ° C. while stirring under a nitrogen stream. While maintaining the temperature at 80 ° C., 781.5 g (7.5 mol) of styrene was added dropwise over 2.5 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, and 28.8 g (1.6 mol) of 10 times the molar amount of the charged lithium amide was added, and the same operation as in Synthesis Example 1 was performed to obtain 1395.6 g of a polyamino composition B.
[0018]
Synthesis Example 3
In a flask similar to Synthesis Example 1, 853.2 g (6.0 mol) of 1,3-bis (aminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company, Ltd .; hereinafter, referred to as 1,3-BAC) and lithium amide 3 0.0 g (0.13 mol) was charged, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, and 23.4 g (1.3 mol) of a 10-fold molar amount of the charged lithium amide was added, and the same operation as in Synthesis Example 1 was performed to obtain 1409.3 g of a polyamino composition C.
[0019]
Synthesis Example 4
The same flask as in Synthesis Example 1 was charged with 711.0 g (5.0 mol) of 1,3-BAC and 3.7 g (0.16 mol) of lithium amide, and heated to 80 ° C. while stirring under a nitrogen stream. While maintaining the temperature at 80 ° C., 781.5 g (7.5 mol) of styrene was added dropwise over 2.5 hours. After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, and 28.8 g (1.6 mol) of 10 times the molar amount of the charged lithium amide was added, and the same operation as in Synthesis Example 1 was performed to obtain 1424.4 g of a polyamino composition D.
[0020]
Synthesis Example 5
612.9 g (4.5 mol) of MXDA and 423.45 g (4.5 mol) of phenol were charged into the same flask as in Example 1, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream. At 80 ° C., 243.3 g (3.0 mol) of formalin (37% aqueous solution containing 8% methanol) was added dropwise over 1.5 hours. After the completion of the dropwise addition, the temperature was raised to 100 ° C., and the reaction was performed for 1.5 hours. Thereafter, the temperature was raised to 150 ° C. over 2 hours while distilling off water, and the reaction was carried out at the same temperature for 1 hour to obtain 1072.0 g of a modified polyamino compound E by Mannich reaction.
[0021]
Synthesis Example 6
The synthesis was performed in the same manner as in Synthesis Example 5 except that MXDA was changed to 639.9 g (4.5 mol) of 1,3-BAC to obtain 1095.6 g of a modified polyamino compound F.
[0022]
Synthesis Examples 7 to 9
The polyamino composition A shown in Synthesis Example 1 and the modified polyamino compound E shown in Synthesis Example 5 were mixed at the ratio shown in Table 1 to obtain epoxy resin curing agents GI.
[0023]
Synthesis Examples 10 to 12
The polyamino composition B shown in Synthesis Example 2 and the modified polyamino compound E shown in Synthesis Example 5 were mixed at the ratio shown in Table 1 to obtain epoxy resin curing agents J to L.
[0024]
Synthesis Examples 13 to 15
The polyamino composition C shown in Synthesis Example 3 and the modified polyamino compound F shown in Synthesis Example 6 were mixed at the ratio shown in Table 2 to obtain epoxy resin curing agents M to O.
[0025]
Synthesis Examples 16 to 18
The polyamino composition D shown in Synthesis Example 4 and the modified polyamino compound E shown in Synthesis Example 6 were mixed at the ratio shown in Table 2 to obtain epoxy resin curing agents P to R.
[0026]
Examples 1-4
The storage stability of the polyamino compositions A to D obtained in Synthesis Examples 1 to 4 was evaluated. Table 3 shows the evaluation results.
[0027]
Examples 5 to 10
The epoxy resin curing agents G to I shown in Synthesis Examples 7 to 9 and the epoxy resin curing agents J to L shown in Synthesis Examples 10 to 12 were mixed with a bisphenol A liquid epoxy resin (trade name: Epicoat 828, Japan Epoxy Resin Co., Ltd.). )) And the proportions shown in Table 2 to prepare an epoxy resin composition. The pot life of the obtained epoxy resin composition was measured. Table 4 shows the measurement results.
[0028]
Examples 11 to 16
The epoxy resin curing agents M to O shown in Synthesis Examples 13 to 15 and the epoxy resin curing agents P to R shown in Synthesis Examples 16 to 18 were combined with a bisphenol A type liquid epoxy resin (trade name: Epicoat 828, Japan Epoxy Resin Co., Ltd.). )) And the proportions shown in Table 2 to prepare an epoxy resin composition. The pot life of the obtained epoxy resin composition was measured. Table 5 shows the measurement results.
[0029]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
The evaluation of the polyamino composition and the epoxy resin composition was performed by the following method.
<Storage stability>
200 g of the polyamino composition was put in a 225 ml glass bottle, sealed, stored for one month under the conditions of 23 ° C. and 50% RH, and then observed for change in appearance and change in viscosity.
<Pot life>
100 g of the epoxy resin composition was placed in a 300 ml polypropylene cup, allowed to stand at 23 ° C. and 50% RH, and the time required to reach the maximum exothermic temperature was measured.
[0035]
【The invention's effect】
As is evident from the above examples, it is obtained by the addition reaction of the polyamino compound represented by the formula (1) with styrene, which is superior in safety and health and has good storage stability, and is represented by the formula (2) The pot life of the epoxy resin composition can be adjusted by using, as an essential component, a polyamino compound composed of adducts having mutually different side chain groups and mixing with another polyamino compound component. Thereby, an epoxy resin composition having an appropriate pot life according to the purpose can be obtained.
Claims (4)
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