JP2011057743A - Heat-curable epoxy resin composition - Google Patents
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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使用するエポキシ樹脂組成物に関する。 The present invention relates to an epoxy resin composition using a specific polyamino composition as an essential component of an epoxy resin curing agent.
エポキシ樹脂が種々の酸無水物やポリアミノ化合物を硬化剤として混合してエポキシ樹脂組成物として使用されることはよく知られている。酸無水物系硬化剤を使用したエポキシ樹脂組成物は、（１）低粘度で作業性に優れる。（２）配合物の可使時間が比較的長い。（３）エポキシ樹脂硬化物の電気絶縁性、機械的特性、耐熱安定性に優れる、などの特徴を有するが、一方で、酸無水物系硬化剤を使用したエポキシ樹脂組成物を硬化させる際には加熱が必要であり、一般に１００〜１５０℃で硬化させる必要がある。また、酸無水物系硬化剤を使用したエポキシ樹脂組成物の硬化反応は発熱反応であり、反応の進行と共に硬化物の中心温度は１９０℃に達することがあり、硬化発熱による温度上昇が激しい場合には、硬化物にヤケ、ボイド、クラック等が生じるため、主に小型の電気電子部品用途に使用される事が一般的で、大型や肉厚の成形品を製造する際には硬化発熱による温度上昇を避けるため、低温から徐々に加熱していく多段階硬化が必要となり、硬化条件の設定が煩雑になると共に、硬化に要する時間が長くなる。 It is well known that an epoxy resin is used as an epoxy resin composition by mixing various acid anhydrides and polyamino compounds as curing agents. An epoxy resin composition using an acid anhydride curing agent is (1) low viscosity and excellent workability. (2) The pot life is relatively long. (3) The epoxy resin cured product has characteristics such as excellent electrical insulation, mechanical properties, and heat stability, but on the other hand, when curing an epoxy resin composition using an acid anhydride curing agent. Needs to be heated, and generally needs to be cured at 100 to 150 ° C. In addition, the curing reaction of the epoxy resin composition using an acid anhydride curing agent is an exothermic reaction, and the center temperature of the cured product may reach 190 ° C as the reaction proceeds. In general, since burns, voids, cracks, etc. occur in the cured product, it is generally used mainly for small electric and electronic parts. When manufacturing large or thick molded products, In order to avoid an increase in temperature, multi-stage curing in which heating is gradually performed from a low temperature is necessary, and setting of curing conditions becomes complicated and time required for curing becomes long.
一方、各種ポリアミノ化合物を使用した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。特に芳香族アミンは脂肪族アミンと比較して塩基性が小さいので硬化速度も抑制され、加熱硬化において発泡などが抑制され大型の成形が可能となるが、近年では発がん性の疑いから使用量は徐々に減少してきている（非特許文献３参照。）。 On the other hand, epoxy resin compositions using various polyamino compounds are especially used in the paint field such as anticorrosion paints for ships, bridges, land and sea iron structures, lining, reinforcement and repair of concrete structures, flooring of buildings, and water and sewage equipment. Widely used in civil engineering and construction fields such as linings, paving materials and adhesives. In particular, aromatic amines have a lower basicity than aliphatic amines, so the curing rate is also suppressed, and foaming is suppressed in heat curing, enabling large-scale molding, but in recent years the amount used has been suspected of carcinogenicity. It is gradually decreasing (see Non-Patent Document 3).
脂肪族アミンの中でも、下記（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、機械物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。
（１） Ｈ２Ｎ−ＣＨ２−Ａ−ＣＨ２−ＮＨ２
（式（１）中、Ａはフェニレン基である。）
Among the aliphatic amines, the polyamino compound represented by the following formula (1) and the epoxy resin curing agent using the polyamino compound as a raw material are compared with other polyamino compounds and the epoxy resin curing agent using the polyamino compound as a raw material. It has features such as providing an excellent cured resin film, an epoxy resin cured film excellent in gloss and smoothness, and an epoxy resin cured product excellent in water resistance, chemical resistance and mechanical properties.
(1) H 2 N-CH 2 -A-CH 2 -NH 2
(In Formula (1), A is a phenylene group.)
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も硬化速度が速く、特に大型や肉厚の成形品を製造する際には、常温でも部分的に硬化が進行し、成形物の変形や強度低下が発生するという欠点を有している。 However, since 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, the epoxy resin composition has a high curing rate even at room temperature curing. When manufacturing a large-sized or thick molded product, there is a drawback that the curing partially proceeds even at room temperature, and the molded product is deformed or strength is reduced.
（１）式で示される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の硬化速度は緩やかになることが知られている。しかしながらこの方法で得られるエポキシ樹脂組成物の硬化速度は、特に大型や肉厚の成形品を製造する際には十分でなく、さらに、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使用することは少なくなってきている。 (1) It is known that when a synoethylated polyamino compound obtained by a Michael addition reaction between a polyamino compound represented by the formula and acrylonitrile is used as an epoxy resin curing agent, the curing rate of the epoxy resin composition becomes slow. . However, the curing rate of the epoxy resin composition obtained by this method is not sufficient particularly when producing large-sized or thick molded articles, and acrylonitrile is designated as a specific chemical and deleterious substance. In recent years, the use of the polyamino compound has been reduced from the viewpoint of health and safety.
特許文献１で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り得られる、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硬化速度は緩やかになっているが、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、反応によってエステル基が減少するためにエポキシ樹脂組成物の硬化速度抑制効果は小さくなる。 Patent Document 1 relates to a low-viscosity, low-hazardous compound obtained by a Michael addition reaction between a polyamino compound and an unsaturated carboxylic acid ester compound, and an epoxy resin composition using the compound as an epoxy resin curing agent Although the curing rate of the compound is slow, the ester and amide exchange reactions proceed during storage due to the presence of amino groups and ester groups in the compound, resulting in increased viscosity due to the formation of amides and poor storage stability. Since the ester group is reduced by the reaction, the effect of suppressing the curing rate of the epoxy resin composition is reduced.
特許文献２では（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物からなるアミノ化合物が得られ、このアミノ化合物は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記載されているが、未反応の（１）式で示されるポリアミン量によっては、特に大型や肉厚の成形品を製造する際には十分な効果が得られず、硬化時に激しい発熱を伴う場合がある。 In Patent Document 2, an amino compound comprising an addition reaction product of a polyamino compound represented by the formula (1) and styrene is obtained, and when this amino compound is used as an epoxy resin curing agent, the epoxy resin composition has a long pot life. However, depending on the amount of unreacted polyamine represented by the formula (1), a sufficient effect cannot be obtained particularly when manufacturing a large-sized or thick molded product, and intense heat is generated during curing. May be accompanied.
本発明の目的は、従来技術における上記したような課題を解決し、比較的低い加熱硬化条件でも十分に硬化が進行し、大型や肉厚の成形品を製造する際にも過剰な発熱が伴わず、かつ良好な物性を与えるエポキシ樹脂組成物を提供することにある。 The object of the present invention is to solve the above-mentioned problems in the prior art, the curing proceeds sufficiently even under relatively low heat-curing conditions, and excessive heat generation is accompanied even when a large-sized or thick molded product is produced. It is another object of the present invention to provide an epoxy resin composition that gives good physical properties.
本発明者らは鋭意研究を重ねた結果、特定のモル比で下記（１）式で示されたポリアミノ化合物とスチレンを反応させたポリアミノ化合物が、比較的低い硬化温度で十分に硬化が進行し、硬化の際に過剰な発熱が伴わないことを見出し、本発明に到達した。
すなわち、本発明はつぎの通りである。
１． （１）式で示されるポリアミノ化合物Ａ １ｍｏｌに対し、スチレン反応比率１．２ｍｏｌから１．５ｍｏｌ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付加物であるポリアミノ化合物Ｂの混合物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とエポキシ樹脂とを含有するエポキシ樹脂組成物。
（１） Ｈ２Ｎ−ＣＨ２−Ａ−ＣＨ２−ＮＨ２
（式（１）中、Ａはフェニレン基である。）
（２） Ｒ１Ｒ２Ｎ−Ｈ２Ｃ−Ａ−ＣＨ２−ＮＨＲ３
（式（２）中、Ａはフェニレン基であり、Ｒ１〜Ｒ３は水素原子またはフェネチル基である。Ｒ１〜Ｒ３は同一でも異なっていてもよいが、Ｒ１〜Ｒ３の少なくとも１つはフェネチル基である。）
２． 前記エポキシ樹脂硬化剤が前記ポリアミノ化合物Ｂ以外に、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少なくとも１つを含有する第１項記載のエポキシ樹脂組成物。
３． 前記エポキシ樹脂硬化剤がポリアミノ化合物Ｂ以外に、ポリオキシアルキレンポリアミンまたは／およびイソホロンジアミンを含有する第１項記載のエポキシ樹脂組成物。
４． 第１項〜第３項のいずれかに記載のエポキシ樹脂組成物を硬化させて得られるエポキシ樹脂硬化物。
５． 第４項記載のエポキシ樹脂硬化物と繊維からなるエポキシ樹脂複合材料。
６． 第５項記載のエポキシ樹脂複合材料からなる航空機用構成部品。
７． 第５項記載のエポキシ樹脂複合材料を用いた風力発電用風車の構成部品。
８． （１）式で示されるポリアミノ化合物Ａ １ｍｏｌに対し、スチレン反応比率１．２ｍｏｌから１．５ｍｏｌ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付加物であるポリアミノ化合物Ｂの混合物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とエポキシ樹脂とを含有するエポキシ樹脂組成物を４０℃〜１００℃の温度で硬化させることを特徴とするエポキシ樹脂組成物の硬化方法。
（１） Ｈ２Ｎ−ＣＨ２−Ａ−ＣＨ２−ＮＨ２
（式（１）中、Ａはフェニレン基である。）
（２） Ｒ１Ｒ２Ｎ−Ｈ２Ｃ−Ａ−ＣＨ２−ＮＨＲ３
（式（２）中、Ａはフェニレン基であり、Ｒ１〜Ｒ３は水素原子またはフェネチル基である。Ｒ１〜Ｒ３は同一でも異なっていてもよいが、Ｒ１〜Ｒ３の少なくとも１つはフェネチル基である。）
As a result of intensive studies, the inventors of the present invention have sufficiently cured a polyamino compound obtained by reacting styrene with a polyamino compound represented by the following formula (1) at a specific molar ratio at a relatively low curing temperature. The present inventors have found that no excessive heat generation is accompanied during curing, and have reached the present invention.
That is, the present invention is as follows.
1. (1) Polyamino compound B which is obtained by an styrene reaction ratio of 1.2 mol to 1.5 mol with respect to 1 mol of polyamino compound A represented by formula (1) and is an adduct having different side chain group structures represented by formula (2) The epoxy resin composition containing the epoxy resin hardening | curing agent and the epoxy resin containing the polyamino composition which have a mixture of these as an essential component.
(1) H 2 N-CH 2 -A-CH 2 -NH 2
(In Formula (1), A is a phenylene group.)
(2) R 1 R 2 N—H 2 C—A—CH 2 —NHR 3
(In the formula (2), A is a phenylene group, R 1 to R 3 are .R 1 to R 3 is a hydrogen atom or a phenethyl group may be the same or different, at least R 1 to R 3 One is a phenethyl group.)
2. The 1st term | claim in which the said epoxy resin hardening | curing agent contains at least 1 chosen from an aliphatic polyamino compound, an alicyclic polyamino compound, an aromatic polyamino compound, and the modified polyamino compound which uses these as a raw material other than the said polyamino compound B. The epoxy resin composition as described.
3. The epoxy resin composition according to claim 1, wherein the epoxy resin curing agent contains polyoxyalkylene polyamine and / or isophoronediamine in addition to the polyamino compound B.
4). An epoxy resin cured product obtained by curing the epoxy resin composition according to any one of Items 1 to 3.
5. An epoxy resin composite material comprising the cured epoxy resin according to item 4 and fibers.
6). An aircraft component comprising the epoxy resin composite material according to item 5.
7). A component of a wind turbine for wind power generation using the epoxy resin composite material according to item 5.
8). (1) Polyamino compound B which is obtained by an styrene reaction ratio of 1.2 mol to 1.5 mol with respect to 1 mol of polyamino compound A represented by formula (1) and is an adduct having different side chain group structures represented by formula (2) A method for curing an epoxy resin composition, comprising: curing an epoxy resin composition containing an epoxy resin curing agent containing a polyamino composition comprising a mixture of the above and an epoxy resin at a temperature of 40 ° C to 100 ° C. .
(1) H 2 N-CH 2 -A-CH 2 -NH 2
(In Formula (1), A is a phenylene group.)
(2) R 1 R 2 N—H 2 C—A—CH 2 —NHR 3
(In the formula (2), A is a phenylene group, R 1 to R 3 are .R 1 to R 3 is a hydrogen atom or a phenethyl group may be the same or different, at least R 1 to R 3 One is a phenethyl group.)
（１）式で示されるポリアミノ化合物Ａ １ｍｏｌに対し１．２ｍｏｌから１．５ｍｏｌの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付加物であるポリアミノ化合物Ｂの混合物を用いることにより、大型や肉厚の成形品を過剰な発熱を伴わず、比較的低い温度で硬化させることができる。また、得られた硬化物の物性も良好である。 (1) Polyamino compound which is obtained by addition reaction with 1.2 mol to 1.5 mol of styrene with respect to 1 mol of polyamino compound A represented by formula (1), and is an adduct having different side chain groups represented by formula (2) By using the mixture of compound B, a large-sized or thick molded product can be cured at a relatively low temperature without excessive heat generation. Moreover, the physical property of the obtained hardened | cured material is also favorable.
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である。 Examples of the polyamino compound A represented by the formula (1) used in the present invention include orthoxylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis ( Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like. Of these, particularly preferred is metaxylylenediamine.
本発明では、ポリアミノ化合物Ａと付加反応させる化合物としては、あらゆるアルケニル化合物が可能であり、例えばエチレン、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン、デセン、イソブチレン、２−ペンテン、３−メチルー１−ブテン、２−メチルー２−ブテン、２，３−ジメチルー２−ブテン、シクロヘキセン、シクロヘキサジエン、スチレン、ジビニルベンゼン、などがあげられるが、特に好ましいのはスチレンである。 In the present invention, the alkenyl compound can be any compound that undergoes addition reaction with the polyamino compound A, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, isobutylene, 2-pentene, 3-pentene, and the like. Examples include methyl-1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, cyclohexene, cyclohexadiene, styrene, divinylbenzene, and the like, and styrene is particularly preferable.
本発明におけるポリアミノ化合物Ａとスチレンとの反応では、ポリアミノ化合物Ａとスチレンの反応比率はポリアミノ化合物Ａ １ｍｏｌに対するスチレンの反応ｍｏｌ数で表され、反応比率が特定の範囲になることにより所望の効果を示す。つまり、ポリアミノ化合物Ａとスチレンの反応比率が低い場合は未反応のジアミンが多くなることにより、硬化速度が速くなり硬化時の発熱量が大きくなる。一方で反応比率が高い場合はアミノ基の活性水素が少なくなるため、硬化速度は遅くなり硬化時の発熱量は抑えることができるが、硬化物の機械物性は低下する。このため、ポリアミノ化合物Ａとスチレンとの反応ではポリアミノ化合物１ｍｏｌに対してスチレンは１．２ｍｏｌ〜１．５ｍｏｌが好適に用いられ、更に好ましくは１．２５ｍｏｌ〜１．４ｍｏｌで反応される。 In the reaction of polyamino compound A and styrene in the present invention, the reaction ratio of polyamino compound A and styrene is represented by the number of moles of styrene reacted with respect to 1 mol of polyamino compound A. Show. That is, when the reaction ratio between the polyamino compound A and styrene is low, the amount of unreacted diamine increases, so that the curing speed increases and the amount of heat generated during curing increases. On the other hand, when the reaction ratio is high, the active hydrogen of the amino group decreases, so the curing rate is slowed down and the amount of heat generated during curing can be suppressed, but the mechanical properties of the cured product are reduced. For this reason, in the reaction of polyamino compound A and styrene, 1.2 mol to 1.5 mol of styrene is suitably used with respect to 1 mol of polyamino compound, and more preferably 1.25 mol to 1.4 mol.
本発明で使用されるポリアミノ化合物Ｂとは、前記ポリアミノ化合物Ａとスチレンとの付加反応により得られる反応生成物であって、（２）式で示される互いに側鎖基の構成が異なる付加物である。
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のいずれか２つが水素原子であり、残り１つがフェネチル基である付加物（下記（３）式で示される付加物Ｒ−１）、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（下記（４）式、（５）式で示される付加物Ｒ−２、付加物Ｒ−３）、およびいずれもがフェネチル基である付加物（下記（６）式で示される付加物Ｒ−４）、である。本発明では、これらの付加物は硬化時の発熱や得られるエポキシ樹脂硬化物の物性の観点から混合物として用いられる。各付加物単独では所望の効果が得られない。
Here, each adduct having a different side chain group structure is an adduct in which any two of R 1 , R 2 and R 3 are hydrogen atoms and the remaining one is a phenethyl group in the formula (2). (Adduct R-1 represented by the following formula (3)), any two of which are phenethyl groups and the remaining one is hydrogen (the following formula (4), adduct R represented by the formula (5)) -2, adduct R-3), and an adduct in which all are phenethyl groups (adduct R-4 represented by the following formula (6)). In the present invention, these adducts are used as a mixture from the viewpoint of heat generation during curing and physical properties of the resulting cured epoxy resin. The desired effect cannot be obtained with each adduct alone.
本発明において、ポリアミノ化合物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。 In the present invention, when producing the polyamino 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., preferably alkali metal amides (general formula MNRR ′: M is an alkali metal, N is nitrogen, R and R ′ are each independently hydrogen or alkyl A lithium amide (LiNH 2 ).
触媒の使用量は、原料の種類や反応比率、反応温度等の条件により異なるが、通常は原料中に０．０５〜５ｗｔ％であり、好ましくは０．１〜３ｗｔ％である。これより少ない場合は反応速度が小さくなり、またこれより多く用いても反応速度は増大せず、経済的ではない。 The amount of the catalyst used varies depending on conditions such as the type of raw material, the reaction ratio, the reaction temperature, etc., but is usually 0.05 to 5 wt%, preferably 0.1 to 3 wt% in the raw material. When the amount is less than this, the reaction rate becomes small, and when the amount is more than this, the reaction rate does not increase, which is not economical.
本発明における反応温度は、（１）式で示されるポリアミノ化合物Ａの融点以上であれば特に限定はされないが、通常２５℃〜１５０℃であり、好ましくは５０℃〜１００℃である。これより反応温度が低い場合は、（１）式で示されるポリアミノ化合物とスチレンとの反応速度が遅く、逆に反応温度が高い場合は、副生成物としてスチレンの重合物が生成することから、反応比率、触媒の種類と量等に応じて反応温度を選択することが望ましい。 Although the reaction temperature in this invention will not be specifically limited if it is more than melting | fusing point of the polyamino compound A shown by (1) Formula, Usually, it is 25 to 150 degreeC, Preferably it is 50 to 100 degreeC. When the reaction temperature is lower than this, the reaction rate between the polyamino compound represented by the formula (1) and styrene is slow, and conversely, when the reaction temperature is high, a polymer of styrene is generated as a by-product. It is desirable to select the reaction temperature according to the reaction ratio, the type and amount of the catalyst, and the like.
本発明における反応には、（１）式で示されるポリアミノ化合物Ａとスチレン、それに触媒のアルカリ金属アミドが用いられるが、（１）式で示されるポリアミノ化合物Ａとスチレンとの反応は発熱反応であり、反応温度を一定に保つためには発熱により生じる温度上昇を制御する必要がある。またスチレンの重合を抑制するために、スチレンは一定の反応温度の範囲内で滴下して添加することが望ましい。スチレンの滴下に要する時間は特に制限はなく、滴下終了後に反応温度を保つことにより目的の化合物を得ることが可能となる。 In the reaction of the present invention, polyamino compound A represented by the formula (1) and styrene and a catalyst alkali metal amide are used. The reaction between the polyamino compound A represented by the formula (1) and styrene is an exothermic reaction. In order to keep the reaction temperature constant, it is necessary to control the temperature rise caused by heat generation. In order to suppress the polymerization of styrene, it is desirable to add styrene dropwise within a certain reaction temperature range. The time required for dropping styrene is not particularly limited, and the target compound can be obtained by maintaining the reaction temperature after completion of dropping.
反応速度は反応比率、反応温度、触媒の種類と量に大きく支配されるため、反応時間は条件により設定されるべきであるが、反応中に反応液のサンプリングを行ない、ガスクロマトグラフィーや液体クロマトグラフィー等で原料であるスチレンの定量を行ない、未反応のスチレンが１ｗｔ％以下になるまでを反応時間とすることが望ましい。 Since the reaction rate is largely governed by the reaction ratio, reaction temperature, and the type and amount of catalyst, the reaction time should be set according to the conditions, but the reaction solution is sampled during the reaction, and gas chromatography or liquid chromatography is performed. It is desirable that the amount of styrene as a raw material is quantitatively determined by graphing or the like, and the reaction time is set until the unreacted styrene becomes 1 wt% or less.
反応終了後に得られる反応液中には、未反応のポリアミノ化合物Ａ、反応により生成したポリアミノ化合物Ｂ、および触媒のアルカリ金属アミドが含まれる。触媒のアルカリ金属アミドは、塩酸、塩化水素ガス、酢酸などの酸、メタノール、エタノール等のアルコール、あるいは水等を加えてアルカリ金属アミドを除去容易な塩に変えてから濾過することが可能である。例えば水を用いた場合には、アルカリ金属アミドが水酸化物となり、濾過が容易になる。 The reaction solution obtained after completion of the reaction contains unreacted polyamino compound A, polyamino compound B produced by the reaction, and alkali metal amide of the catalyst. The alkali metal amide of the catalyst can be filtered after adding an acid such as hydrochloric acid, hydrogen chloride gas, acetic acid, alcohol such as methanol or ethanol, or water to change the alkali metal amide to a salt that can be easily removed. . For example, when water is used, the alkali metal amide becomes a hydroxide, which facilitates filtration.
本発明において、ポリアミノ組成物は前記ポリアミノ化合物Ｂの混合物を必須成分とするが、未反応のポリアミノ化合物Ａを含んでいてもよい。ポリアミノ組成物中の未反応のポリアミノ化合物Ａの含有量は３〜１５重量％、好ましくは５〜１２重量％、より好ましくは７〜１２重量％である。 In the present invention, the polyamino composition contains a mixture of the polyamino compound B as an essential component, but may contain an unreacted polyamino compound A. The content of the unreacted polyamino compound A in the polyamino composition is 3 to 15% by weight, preferably 5 to 12% by weight, more preferably 7 to 12% by weight.
本発明において、ポリアミノ組成物は前記ポリアミノ化合物Ｂの混合物を必須成分として含むものであるが、ポリアミノ組成物にはポリアミノ化合物Ｂ以外に他のポリアミノ化合物を加えてもよい。例えば、ジエチレントリアミン（ＤＥＴＡ）、トリエチレンテトラミン（ＴＥＴＡ）、テトラエチレンペンタミン（ＴＥＰＡ）等の脂肪族ポリアミノ化合物、イソホロンジアミン（ＩＰＤＡ）、ノルボルネンジアミン（ＮＢＤＡ）等の脂環族ポリアミノ化合物、ポリオキシエチレンジアミン、ポリオキシプロピレンジアミン、ポリオキシテトラメチレンジアミン、ポリ（オキシエチレン−オキシプロピレン）ジアミン等のポリオキシアルキレンジアミン、あるいはポリオキシエチレントリアミン、ポリオキシプロピレントリアミン等ポリオキシアルキレンポリアミン。フェニレンジアミン、ジアミノジフェニルメタン（ＤＤＭ）等の芳香族ポリアミノ化合物から選ばれるが、特に硬化速度の観点からイソホロンジアミン、ポリオキシプロピレンジアミンが好適に用いられる。 In the present invention, the polyamino composition contains the mixture of the polyamino compound B as an essential component, but other polyamino compounds may be added to the polyamino composition in addition to the polyamino compound B. For example, aliphatic polyamino compounds such as diethylenetriamine (DETA), triethylenetetramine (TETA) and tetraethylenepentamine (TEPA), alicyclic polyamino compounds such as isophoronediamine (IPDA) and norbornenediamine (NBDA), polyoxyethylenediamine Polyoxyalkylene diamines such as polyoxypropylene diamine, polyoxytetramethylene diamine and poly (oxyethylene-oxypropylene) diamine, or polyoxyalkylene polyamines such as polyoxyethylene triamine and polyoxypropylene triamine. Although selected from aromatic polyamino compounds such as phenylenediamine and diaminodiphenylmethane (DDM), isophoronediamine and polyoxypropylenediamine are particularly preferably used from the viewpoint of curing speed.
ポリアミノ化合物Ｂ以外の他のポリアミノ化合物として、上記のポリアミノ化合物を変性して変性ポリアミノ化合物として使用する場合には、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等の方法が挙げられ、変性の方法は特に限定されないが、エポキシ化合物との反応による変性が好適に用いられる。 In the case of using the above polyamino compound as a modified polyamino compound as a polyamino compound other than the polyamino compound B, modification by a Mannich reaction between a phenolic compound and an aldehyde compound, modification by reaction with an epoxy compound, Examples of the modification include a modification by reaction with a compound having a carboxyl group and a modification by Michael reaction with an acrylic compound. The modification method is not particularly limited, but modification by reaction with an epoxy compound is preferably used.
本発明におけるエポキシ樹脂硬化剤には、ポリアミノ化合物Ｂの混合物を必須成分とする前記ポリアミノ組成物と必要に応じて各種添加剤を加えることができる。 In the epoxy resin curing agent of the present invention, the polyamino composition containing a mixture of the polyamino compound B as an essential component and various additives as necessary can be added.
本発明のエポキシ樹脂組成物は、エポキシ樹脂と前記エポキシ樹脂硬化剤を含むものである。本発明のエポキシ樹脂組成物に使用されるエポキシ樹脂は、本発明のエポキシ樹脂硬化剤のアミノ基由来の活性水素と反応し架橋することが可能なグリシジル基を持つエポキシ樹脂で、飽和または不飽和の脂肪族化合物や、脂環式化合物、芳香族化合物、あるいは複素環式化合物のいずれであってよい。具体的には、ビスフェノールＡから誘導されたグリシジルエーテル部位を有するエポキシ樹脂、ビスフェノールＦ型から誘導されたグリシジルエーテル部位を有するエポキシ樹脂、メタキシリレンジアミンから誘導されたグリシジルアミン部位を有するエポキシ樹脂、１，３−ビス（アミノメチル）シクロヘキサンから誘導されたグリシジルアミン部位を有するエポキシ樹脂、ジアミノジフェニルメタンから誘導されたグリシジルアミン部位を有するエポキシ樹脂、パラアミノフェノールから誘導されたグリシジルアミン部位を有するエポキシ樹脂、フェノールノボラックから誘導されたグリシジルエーテル部位を有するエポキシ樹脂、およびレゾルシノールから誘導されたグリシジルエーテル部位を有するエポキシ樹脂から選ばれる少なくとも１つの樹脂が挙げられる。この中でもビスフェノールＡから誘導されたグリシジルエーテル部位を有するエポキシ樹脂、ビスフェノールＦ型から誘導されたグリシジルエーテル部位を有するエポキシ樹脂が特に好ましい。 The epoxy resin composition of this invention contains an epoxy resin and the said epoxy resin hardening | curing agent. The epoxy resin used in the epoxy resin composition of the present invention is an epoxy resin having a glycidyl group capable of reacting with the active hydrogen derived from the amino group of the epoxy resin curing agent of the present invention and capable of crosslinking, and is saturated or unsaturated. Any of the aliphatic compounds, alicyclic compounds, aromatic compounds, and heterocyclic compounds may be used. Specifically, an epoxy resin having a glycidyl ether moiety derived from bisphenol A, an epoxy resin having a glycidyl ether moiety derived from bisphenol F type, an epoxy resin having a glycidyl amine moiety derived from metaxylylenediamine, An epoxy resin having a glycidylamine moiety derived from 1,3-bis (aminomethyl) cyclohexane, an epoxy resin having a glycidylamine moiety derived from diaminodiphenylmethane, an epoxy resin having a glycidylamine moiety derived from paraaminophenol, At least selected from an epoxy resin having a glycidyl ether moiety derived from phenol novolac and an epoxy resin having a glycidyl ether moiety derived from resorcinol Also it includes one resin. Of these, epoxy resins having a glycidyl ether moiety derived from bisphenol A and epoxy resins having a glycidyl ether moiety derived from bisphenol F type are particularly preferred.
本発明のエポキシ樹脂組成物は、前記エポキシ樹脂と前記エポキシ樹脂硬化剤を含むものである。さらに本発明のエポキシ樹脂組成物には用途に応じて充填材、可塑剤などの改質成分、反応性又は非反応性の希釈剤、揺変性付与材などの流動調整成分、顔料、粘着付与剤などの成分やハジキ防止剤、流展剤、消泡剤、紫外線吸収剤、光安定剤、硬化促進剤などの添加剤を本発明の効果を損なわない範囲で用いることができる。 The epoxy resin composition of the present invention contains the epoxy resin and the epoxy resin curing agent. Furthermore, the epoxy resin composition of the present invention includes a filler, a modifying component such as a plasticizer, a reactive or non-reactive diluent, a flow regulating component such as a thixotropic agent, a pigment, and a tackifier. And other components such as anti-repellent agents, spreading agents, antifoaming agents, ultraviolet absorbers, light stabilizers and curing accelerators can be used as long as the effects of the present invention are not impaired.
本発明におけるエポキシ樹脂硬化剤の配合量は、エポキシ樹脂のエポキシ当量に対して、本発明のエポキシ樹脂硬化剤の活性水素当量が０．７〜１．０となる量が好ましい。本発明におけるエポキシ樹脂硬化剤の活性水素当量が０．７未満であると、硬化物の架橋度が不十分であり、また１．０を越えると親水性のアミノ基が過多となり、耐水性が損なわれる。 The compounding amount of the epoxy resin curing agent in the present invention is preferably such that the active hydrogen equivalent of the epoxy resin curing agent of the present invention is 0.7 to 1.0 with respect to the epoxy equivalent of the epoxy resin. When the active hydrogen equivalent of the epoxy resin curing agent in the present invention is less than 0.7, the degree of crosslinking of the cured product is insufficient, and when it exceeds 1.0, the hydrophilic amino group is excessive and the water resistance is improved. Damaged.
前記エポキシ樹脂組成物を硬化させエポキシ樹脂硬化物を製造する方法としては、例えばエポキシ樹脂組成物をそのまま所定温度まで加熱して硬化させる方法、前記エポキシ樹脂組成物を金型等に注ぎ、該金型をさらに加熱して成形する方法、前記エポキシ樹脂組成物を溶融させ、得られる溶融物を予め加熱された金型に注入し硬化する方法、前記エポキシ樹脂組成物を部分硬化させ、得られる部分硬化物を粉砕してなる粉末を金型に充填し、該充填粉末を溶融成形する方法、前記エポキシ樹脂組成物を必要に応じて溶媒に溶解し、攪拌しながら部分硬化させ、得られた溶液をキャストした後、溶媒を通風乾燥等で乾燥除去し、必要に応じてプレス機等で圧力をかけながら所定時間加熱する方法等が挙げられる。硬化時に加熱する温度は、加熱により成形品にヤケやクラックなどの強度低下が発生しない温度であれば特に限定されないが、好ましくは４０〜１００℃、更に好ましくは５０〜８０℃で硬化される。 Examples of a method for producing an epoxy resin cured product by curing the epoxy resin composition include, for example, a method of curing an epoxy resin composition by heating it to a predetermined temperature as it is, pouring the epoxy resin composition into a mold or the like, Method of further heating the mold, molding the epoxy resin composition, injecting the resulting melt into a preheated mold and curing, part of the epoxy resin composition being partially cured A method of filling a mold with a powder obtained by pulverizing a cured product, melt-molding the filled powder, dissolving the epoxy resin composition in a solvent as necessary, and partially curing with stirring to obtain a solution And a method of heating and drying for a predetermined time while applying pressure with a press machine or the like, if necessary. The temperature to be heated at the time of curing is not particularly limited as long as it is a temperature at which strength reduction such as burns and cracks does not occur in the molded product by heating, but it is preferably cured at 40 to 100 ° C, more preferably at 50 to 80 ° C.
本発明のエポキシ樹脂複合材料は、エポキシ樹脂組成物と繊維基材からなり、繊維基材としては、ガラス、ボロン繊維織布等の無機質繊維の織布もしくは不織布、ポリエステル、アラミド等の有機質繊維の織布もしくは不織布等が挙げられる。具体的にはストランド、織物、マット、ニット、ブレイドなどの強化繊維基材を、樹脂注入に先立ち型内に配置する。強化繊維基材は、所望の形状に裁断、積層して、必要で有ればコア材等の、その他の材料と共に直接型内に配置してもよい。さらには、裁断、積層後、ステッチや、少量の結着性樹脂を付与して加熱・加圧する方法等により、強化繊維基材を所望の形状に賦形したプリフォームを型内に配置してもよい。また、プリフォームには強化繊維基材と、コア材等の強化繊維基材以外の材料とを組みあわせたものを用いることもできる。 The epoxy resin composite material of the present invention comprises an epoxy resin composition and a fiber base material, and the fiber base material is a woven or non-woven fabric of inorganic fibers such as glass or boron fiber woven fabric, or organic fibers such as polyester or aramid. Examples thereof include a woven fabric and a non-woven fabric. Specifically, reinforcing fiber substrates such as strands, woven fabrics, mats, knits, and blades are placed in the mold prior to resin injection. The reinforcing fiber base material may be cut and laminated into a desired shape, and if necessary, placed directly in the mold together with other materials such as a core material. Furthermore, after cutting and laminating, a preform with a reinforcing fiber substrate shaped into a desired shape is placed in the mold by a method such as stitching or applying a small amount of binder resin and heating / pressing. Also good. Moreover, what combined the reinforcing fiber base material and materials other than reinforcing fiber base materials, such as a core material, can also be used for a preform.
本発明のエポキシ複合材料を用いた航空機用構成部品としては、航空機の先端ドーム、前足扉、エンジンカウリング、主翼前縁、主翼後縁パネル、フラップ外板、フラップ内板、フラップペロン、エルロン外板、フェアリング、方向舵、昇降舵、床梁等が挙げられる。 The aircraft components using the epoxy composite material of the present invention include aircraft dome, front foot door, engine cowling, main wing leading edge, main wing trailing edge panel, flap outer plate, flap inner plate, flap peron, aileron outer plate. , Fairing, rudder, elevator, floor beam and the like.
本発明の風力発電用風車としては、プロペラ型、セイルウイング型、オランダ型、多翼型、ダリウス型、ジャイロミル型、直線翼型、サボニウス型、パドル型、クロスフロー型、Ｓ型ローター型がある。また構成部品としては風車翼、ナセルカバー等を挙げることができる。 Examples of wind turbines for wind power generation according to the present invention include propeller type, sail wing type, Dutch type, multi-wing type, Darius type, gyro mill type, straight wing type, Savonius type, paddle type, cross flow type, S type rotor type. is there. Examples of components include wind turbine blades and nacelle covers.
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。尚、本実施例及び比較例で採用した評価法は以下の通りである。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the evaluation method employ | adopted by the present Example and the comparative example is as follows.
（１）未反応アミン
ガスクロマトグラフィー（以下、ＧＣ分析）を用いて分析した。
カラム；クロムパック（株）製 ＣＰ−Ｓｉｌ８ＣＢ ｆｏｒ Ａｍｉｎｅ（長さ３０ｍ、Ｆｉｌｍ厚０．２５μｍ、内径０．３５ｍｍ）、カラム温度；１３０℃／２０分
（２）各付加物
ガスクロマトグラフィー（以下、ＧＣ分析）を用いて分析した。
カラム；クロムパック（株）製 ＣＰ−Ｓｉｌ８ＣＢ ｆｏｒ Ａｍｉｎｅ（長さ３０ｍ、Ｆｉｌｍ厚０．２５μｍ、内径０．３５ｍｍ）、カラム温度；１３０℃／２０分→（１０℃／分）→３００℃／３０分
（２）硬化発熱温度の測定
エポキシ樹脂組成物３００ｇを５００ｍｌポリプロピレン製カップに入れ、５０℃、５０％ＲＨの条件下に放置し、硬化発熱温度を測定した。
（３）ガラス転移点（Ｔｇ）の測定
装置は島津製作所製ＤＳＣ−６０を使用した。各試料をＤＳＣ測定パンに仕込み、窒素雰囲気下にて昇温速度１０℃／分で、２００℃まで昇温した後に冷却した後に測定を行った。
（４）硬化物の機械物性評価
エポキシ樹脂組成物を、２３℃、５０％ＲＨの条件下で、７日間硬化させて各試験片を作製した。引張強度をＪＩＳ Ｋ ７１１３に準拠して評価した。
(1) Unreacted amine It analyzed using gas chromatography (henceforth GC analysis).
Column: CP-Sil8CB for Amine (length 30 m, Film thickness 0.25 μm, inner diameter 0.35 mm) manufactured by Chrome Pack Co., Ltd., column temperature: 130 ° C./20 minutes (2) Each adduct gas chromatography (hereinafter, GC analysis).
Column: CP-Sil8CB for Amine (length 30 m, Film thickness 0.25 μm, inner diameter 0.35 mm) manufactured by Chrome Pack Co., Ltd., column temperature: 130 ° C./20 minutes → (10 ° C./min)→300° C./30 Minute (2) Measurement of Curing Exothermic Temperature 300 g of the epoxy resin composition was put in a 500 ml polypropylene cup and left under conditions of 50 ° C. and 50% RH, and the curing exothermic temperature was measured.
(3) Measurement of glass transition point (Tg) The apparatus used was DSC-60 manufactured by Shimadzu Corporation. Each sample was placed in a DSC measurement pan, measured at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, cooled to 200 ° C., and then measured.
(4) Mechanical property evaluation of hardened | cured material The epoxy resin composition was hardened on the conditions of 23 degreeC and 50% RH for 7 days, and each test piece was produced. The tensile strength was evaluated according to JIS K7113.
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、１３８０．７ｇのポリアミノ組成物Ｃ−１を得た。ＧＣ分析の結果、該ポリアミノ組成物中の各付加物および未反応ＭＸＤＡの割合はつぎの通りであった。
Ｒ−１：５６．９ｗｔ％、Ｒ−２：２１．９ｗｔ％、Ｒ−３：３．１ｗｔ％、Ｒ−４：２．４ｗｔ％、未反応ＭＸＤＡ：１５．７ｗｔ％。
Synthesis example 1
Metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as MXDA) 817.2 g (6.0 mol) in a 2 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and condenser tube And 2.9 g (0.13 mol) of lithium amide (Merk reagent) were charged, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining the temperature at 80 ° C., 625.2 g (6.0 mol) of styrene (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade) was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour.
Thereafter, the mixture was cooled to room temperature, and 23.4 g (1.3 mol) of water having a 10-fold molar amount of the charged lithium amide was added and stirred. After the precipitate in the liquid in the flask was separated by filtration, water was distilled off by distillation under reduced pressure to obtain 1380.7 g of polyamino composition C-1. As a result of GC analysis, the ratio of each adduct and unreacted MXDA in the polyamino composition was as follows.
R-1: 56.9 wt%, R-2: 21.9 wt%, R-3: 3.1 wt%, R-4: 2.4 wt%, unreacted MXDA: 15.7 wt%.
合成例２
合成例１と同様のフラスコにＭＸＤＡ６８１．０ｇ（５．０モル）とリチウムアミド２．６ｇ（０．１１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６２４．０ｇ（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１９．８ｇ（１．１モル）を加え、合成例１と同様の操作を行い、１２３９ｇのポリアミノ組成物Ｃ−２を得た。ＧＣ分析の結果、該ポリアミノ組成物中の各付加物および未反応ＭＸＤＡの割合はつぎの通りであった。
Ｒ−１：４１．６ｗｔ％、Ｒ−２：３５．９ｗｔ％、Ｒ−３：４．７ｗｔ％、Ｒ−４：６．６ｗｔ％、未反応ＭＸＤＡ：１１．２ｗｔ％。
Synthesis example 2
MXDA 681.0 g (5.0 mol) and lithium amide 2.6 g (0.11 mol) were charged in the same flask as in Synthesis Example 1, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining the temperature at 80 ° C., 624.0 g (6.0 mol) of styrene was dropped over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, 19.8 g (1.1 mol) of water having 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 1239 g of polyamino composition C-2. . As a result of GC analysis, the ratio of each adduct and unreacted MXDA in the polyamino composition was as follows.
R-1: 41.6 wt%, R-2: 35.9 wt%, R-3: 4.7 wt%, R-4: 6.6 wt%, unreacted MXDA: 11.2 wt%.
合成例３
合成例１と同様のフラスコにＭＸＤＡ６８１．０ｇ（５．０モル）とリチウムアミド２．７ｇ（０．１２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６７６ｇ（６．５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２１．３ｇ（１．２モル）を加え、合成例１と同様の操作を行い、１２８９．１ｇのポリアミノ組成物Ｃ−３を得た。ＧＣ分析の結果、該ポリアミノ組成物中の各付加物および未反応ＭＸＤＡの割合はつぎの通りであった。
Ｒ−１：４０．９ｗｔ％、Ｒ−２：３７．６ｗｔ％、Ｒ−３：５．２ｗｔ％、Ｒ−４：７．８ｗｔ％、未反応ＭＸＤＡ：８．５ｗｔ％。
Synthesis example 3
MXDA 681.0 g (5.0 mol) and lithium amide 2.7 g (0.12 mol) were charged into the same flask as in Synthesis Example 1, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining the temperature at 80 ° C., 676 g (6.5 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, 21.3 g (1.2 mol) of 10-fold molar amount of the charged lithium amide was added, and the same operation as in Synthesis Example 1 was performed to obtain 1289.1 g of polyamino composition C-3. Obtained. As a result of GC analysis, the ratio of each adduct and unreacted MXDA in the polyamino composition was as follows.
R-1: 40.9 wt%, R-2: 37.6 wt%, R-3: 5.2 wt%, R-4: 7.8 wt%, unreacted MXDA: 8.5 wt%.
合成例４
合成例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２２．９ｇ（１．３モル）を加え、合成例１と同様の操作を行い、１３９５．６ｇのポリアミノ組成物Ｃ−４を得た。ＧＣ分析の結果、該ポリアミノ組成物中の各付加物および未反応ＭＸＤＡの割合はつぎの通りであった。
Ｒ−１：３７．２ｗｔ％、Ｒ−２：４１．８ｗｔ％、Ｒ−３：５．３ｗｔ％、Ｒ−４：１０．３ｗｔ％、未反応ＭＸＤＡ：５．４ｗｔ％。
Synthesis example 4
MXDA 681.0 g (5.0 mol) and lithium amide 2.9 g (0.13 mol) were charged into the same flask as in Synthesis Example 1, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining at 80 ° C., 781.5 g (7.5 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, water (22.9 g, 1.3 mol) of 10-fold 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 polyamino composition C-4. Obtained. As a result of GC analysis, the ratio of each adduct and unreacted MXDA in the polyamino composition was as follows.
R-1: 37.2 wt%, R-2: 41.8 wt%, R-3: 5.3 wt%, R-4: 10.3 wt%, unreacted MXDA: 5.4 wt%.
合成例５
合成例１と同様のフラスコにＭＸＤＡ６８１．０ｇ（５．０モル）とリチウムアミド３．４ｇ（０．１５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１０４０ｇ（１０．０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２７．０ｇ（１．５モル）を加え、合成例１と同様の操作を行い、１６３０．５ｇのポリアミノ組成物Ｃ−５を得た。ＧＣ分析の結果、該ポリアミノ組成物中の各付加物および未反応ＭＸＤＡの割合はつぎの通りであった。
Ｒ−１：１２．１ｗｔ％、Ｒ−２：４７．８ｗｔ％、Ｒ−３：４．１ｗｔ％、Ｒ−４：３１．４ｗｔ％、その他：３．５％、未反応ＭＸＤＡ：１．１ｗｔ％。
Synthesis example 5
MXDA 681.0 g (5.0 mol) and lithium amide 3.4 g (0.15 mol) were charged into the same flask as in Synthesis Example 1, and the temperature was raised to 80 ° C. with stirring in a nitrogen stream. While maintaining the temperature at 80 ° C., 1040 g (10.0 mol) of styrene was added dropwise over 2.5 hours. After completion of dropping, the mixture was kept at 80 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, 27.0 g (1.5 mol) of 10-fold molar amount of the charged lithium amide was added, and the same operation as in Synthesis Example 1 was performed to obtain 1630.5 g of polyamino composition C-5. Obtained. As a result of GC analysis, the ratio of each adduct and unreacted MXDA in the polyamino composition was as follows.
R-1: 12.1 wt%, R-2: 47.8 wt%, R-3: 4.1 wt%, R-4: 31.4 wt%, others: 3.5%, unreacted MXDA: 1.1 wt %.
実施例１〜３
合成例２〜４で得られたポリアミノ組成物Ｃ−２〜Ｃ−４をそのままエポキシ樹脂硬化剤として使用し、それぞれエポキシ樹脂硬化剤Ｄ−２〜Ｄ−４とし、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、エポキシ当量１８６、ジャパンエポキシレジン（株）製）と表１に示す割合で混合し、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最高発熱温度、硬化性およびエポキシ樹脂硬化塗膜の外観を評価した。評価結果を表１に示す。
Examples 1-3
The polyamino compositions C-2 to C-4 obtained in Synthesis Examples 2 to 4 were used as they were as epoxy resin curing agents, respectively, and were used as epoxy resin curing agents D-2 to D-4, respectively, and bisphenol A type liquid epoxy resins ( Product name: Epicoat 828, epoxy equivalent 186, manufactured by Japan Epoxy Resin Co., Ltd.) and the ratio shown in Table 1 were mixed to prepare an epoxy resin composition. The obtained exothermic resin composition was evaluated for maximum exothermic temperature, curability and appearance of the cured epoxy resin coating. The evaluation results are shown in Table 1.
比較例１、２
合成例１、５で得られたポリアミノ組成物Ｃ−１、Ｃ−５をそのままエポキシ樹脂硬化剤として使用し、それぞれエポキシ樹脂硬化剤Ｄ−１、Ｄ−５とし、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、エポキシ当量１８６、ジャパンエポキシレジン（株）製）と表１に示す割合で混合し、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最高発熱温度、硬化性およびエポキシ樹脂硬化塗膜の外観を評価した。評価結果を表２に示す。
Comparative Examples 1 and 2
The polyamino compositions C-1 and C-5 obtained in Synthesis Examples 1 and 5 were used as epoxy resin curing agents as they were, respectively, and epoxy resin curing agents D-1 and D-5, respectively, and bisphenol A type liquid epoxy resin ( Product name: Epicoat 828, epoxy equivalent 186, manufactured by Japan Epoxy Resin Co., Ltd.) and the ratio shown in Table 1 were mixed to prepare an epoxy resin composition. The obtained exothermic resin composition was evaluated for maximum exothermic temperature, curability and appearance of the cured epoxy resin coating. The evaluation results are shown in Table 2.
本発明のエポキシ樹脂組成物は、大型や肉厚の成形品を過剰な発熱を伴わず、比較的低い温度で硬化させることができる。また得られたエポキシ樹脂硬化物も高い物性を有することから加熱硬化型樹脂組成物として有用なものであり、工業的価値は高い。 The epoxy resin composition of the present invention can cure a large or thick molded article without excessive heat generation at a relatively low temperature. Moreover, since the obtained epoxy resin cured product also has high physical properties, it is useful as a thermosetting resin composition and has high industrial value.
Claims (8)
（１） Ｈ２Ｎ−ＣＨ２−Ａ−ＣＨ２−ＮＨ２
（式（１）中、Ａはフェニレン基である。）
（２） Ｒ１Ｒ２Ｎ−Ｈ２Ｃ−Ａ−ＣＨ２−ＮＨＲ３
（式（２）中、Ａはフェニレン基であり、Ｒ１〜Ｒ３は水素原子またはフェネチル基である。Ｒ１〜Ｒ３は同一でも異なっていてもよいが、Ｒ１〜Ｒ３の少なくとも１つはフェネチル基である。） Polyamino compound B, which is an adduct obtained by formula (2) and having different side chain groups, is obtained at a styrene reaction ratio of 1.2 mol to 1.5 mol with respect to 1 mol of polyamino compound A represented by formula (1). The epoxy resin composition containing the epoxy resin hardening | curing agent and the epoxy resin containing the polyamino composition which have a mixture of these as an essential component.
(1) H 2 N-CH 2 -A-CH 2 -NH 2
(In Formula (1), A is a phenylene group.)
(2) R 1 R 2 N—H 2 C—A—CH 2 —NHR 3
(In the formula (2), A is a phenylene group, R 1 to R 3 are .R 1 to R 3 is a hydrogen atom or a phenethyl group may be the same or different, at least R 1 to R 3 One is a phenethyl group.)
（１） Ｈ２Ｎ−ＣＨ２−Ａ−ＣＨ２−ＮＨ２
（式（１）中、Ａはフェニレン基である。）
（２） Ｒ１Ｒ２Ｎ−Ｈ２Ｃ−Ａ−ＣＨ２−ＮＨＲ３
（式（２）中、Ａはフェニレン基であり、Ｒ１〜Ｒ３は水素原子またはフェネチル基である。Ｒ１〜Ｒ３は同一でも異なっていてもよいが、Ｒ１〜Ｒ３の少なくとも１つはフェネチル基である。） Polyamino compound B, which is an adduct obtained by formula (2) and having different side chain groups, is obtained at a styrene reaction ratio of 1.2 mol to 1.5 mol with respect to 1 mol of polyamino compound A represented by formula (1). A method for curing an epoxy resin composition, comprising: curing an epoxy resin composition containing an epoxy resin curing agent containing a polyamino composition comprising a mixture of the above and an epoxy resin at a temperature of 40 ° C to 100 ° C. .
(1) H 2 N-CH 2 -A-CH 2 -NH 2
(In Formula (1), A is a phenylene group.)
(2) R 1 R 2 N—H 2 C—A—CH 2 —NHR 3
(In the formula (2), A is a phenylene group, R 1 to R 3 are .R 1 to R 3 is a hydrogen atom or a phenethyl group may be the same or different, at least R 1 to R 3 One is a phenethyl group.)
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| JP2004018711A (en) * | 2002-06-18 | 2004-01-22 | Mitsubishi Gas Chem Co Inc | Method for controlling pot life of epoxy resin composition |
| JP2004075989A (en) * | 2002-06-18 | 2004-03-11 | Mitsubishi Gas Chem Co Inc | Amino composition and method for producing the same |
| JP2007197702A (en) * | 2005-12-28 | 2007-08-09 | Mitsubishi Gas Chem Co Inc | Epoxy resin-curing agent and epoxy resin composition |
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| JP2004018711A (en) * | 2002-06-18 | 2004-01-22 | Mitsubishi Gas Chem Co Inc | Method for controlling pot life of epoxy resin composition |
| JP2004075989A (en) * | 2002-06-18 | 2004-03-11 | Mitsubishi Gas Chem Co Inc | Amino composition and method for producing the same |
| JP2007197702A (en) * | 2005-12-28 | 2007-08-09 | Mitsubishi Gas Chem Co Inc | Epoxy resin-curing agent and epoxy resin composition |
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