JP2006131661A - Epoxy resin composition and epoxy resin-cured material - Google Patents
Epoxy resin composition and epoxy resin-cured material Download PDFInfo
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Abstract
Description
本発明は、ポリテトラメチレンエーテルグリコールのジグリシジルエーテルを単独またはポリテトラメチレンエーテルグリコールのジグリシジルエーテルとビスフェノール型エポキシ樹脂から成るエポキシ樹脂と、特定のアミン系硬化剤が配合されたエポキシ樹脂組成物およびエポキシ樹脂硬化体に関するものであり、その硬化物はゴム弾性を有し、低温柔軟性、接着性に優れるため、シーリング剤、接着剤、コーティング剤、熱硬化型エラストマー等の用途で有用である。 The present invention relates to an epoxy resin composition in which a diglycidyl ether of polytetramethylene ether glycol alone or an epoxy resin composed of a diglycidyl ether of polytetramethylene ether glycol and a bisphenol type epoxy resin and a specific amine curing agent are blended. In addition, the cured product has rubber elasticity and is excellent in low-temperature flexibility and adhesiveness. Therefore, it is useful in applications such as sealing agents, adhesives, coating agents, and thermosetting elastomers. .
エポキシ樹脂は、耐熱性、接着性、耐水性、機械的強度及び電気特性等に優れていることから、接着剤、塗料、土木建築用材料、電気・電子部品の絶縁材料等、様々の分野で使用されている。常温又は加熱硬化型のエポキシ樹脂としては、ビスフェノ−ルＡのジグリシジルエ−テル、ビスフェノ−ルＦのジグリシジルエ−テル、フェノ−ル又はクレゾールノボラック型エポキシ樹脂等の芳香族エポキシ樹脂が一般的である。 Epoxy resins are excellent in heat resistance, adhesion, water resistance, mechanical strength, electrical properties, etc., so they are used in various fields such as adhesives, paints, materials for civil engineering and construction, insulating materials for electrical and electronic parts, etc. in use. As the normal temperature or heat-curing type epoxy resin, aromatic epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, phenol or cresol novolac type epoxy resin are generally used.
エポキシ樹脂はこのように様々な化学構造と優れた性質を有する樹脂であるが、近年、各種用途における要求性能が高まるにつれて種々の改良すべき点が明らかになってきた。その一つにエポキシ樹脂は硬く脆いという点が挙げられる。すなわちビスフェノールＡ型に代表されるエポキシ樹脂は一般に柔軟性に乏しく、特に弾性体のコーティング材料、シーリング剤として用いた場合にはクラックが生じ易く、工業上使用できないという問題があった。 Epoxy resins are resins having various chemical structures and excellent properties as described above, but in recent years, various points to be improved have become clear as the required performance in various applications increases. One of them is that epoxy resins are hard and brittle. That is, the epoxy resin represented by the bisphenol A type is generally poor in flexibility, and particularly when used as an elastic coating material or a sealing agent, there is a problem that cracks are likely to occur and it cannot be used industrially.
このような事情からエポキシ樹脂に可撓性を付与する検討が今も活発に行われている。その中でカルボキシル基末端ブタジエン・アクリロニトリルコポリマー（CTBN）等のエラストマーや熱可塑性弾性体をエポキシ樹脂中にブレンドし可撓性を向上させる方法、またはダイマー酸のジグリシジルエステル、ポリプロピレングリコールのジグリシジルエーテル等の分子内に柔軟性骨格を有する可撓性エポキシ樹脂を添加する方法が知られている。 Under such circumstances, studies for imparting flexibility to epoxy resins are still being actively conducted. Among them, an elastomer such as carboxyl-terminated butadiene / acrylonitrile copolymer (CTBN) or a thermoplastic elastomer is blended into an epoxy resin to improve flexibility, or diglycidyl ester of dimer acid, diglycidyl ether of polypropylene glycol A method of adding a flexible epoxy resin having a flexible skeleton in the molecule is known.
しかし、弾性体を添加する方法は、エポキシ樹脂に弾性体を適当な粒径でしかも再現性よく分散させることが必要であることから技術的困難性が大きく、工業上極めて難しい。また、可撓性エポキシを添加する方法は、単に硬化物を柔らかくするだけで、硬化物の機械的特性、特に反発弾性特性が不十分であるため、満足する弾性体を有する硬化物が得られていない。 However, the method of adding an elastic body has great technical difficulty because it is necessary to disperse the elastic body in an epoxy resin with an appropriate particle size and with good reproducibility, and is extremely difficult industrially. In addition, the method of adding a flexible epoxy simply softens the cured product, and the cured product has insufficient mechanical properties, particularly rebound resilience, so that a cured product having a satisfactory elastic body can be obtained. Not.
そこで、ビスフェノール化合物とジビニルエーテルの反応生成物をエピクロルヒドリンでエポキシ化した可撓性を有するエポキシ樹脂が提案されている（特許文献１）。
しかし、このエポキシ樹脂は可撓性に優れるがゴム状の弾性を示すまでに至らず、更に引っ張り伸びが小さいため、繰り返し屈曲性を要求される用途には不向きであった。
Then, the flexible epoxy resin which epoxidized the reaction product of the bisphenol compound and divinyl ether with epichlorohydrin is proposed (patent document 1).
However, this epoxy resin is excellent in flexibility but does not exhibit rubber-like elasticity, and further has a small tensile elongation, so it is unsuitable for applications that require repeated bendability.
他方、ポリテトラメチレンエーテルグリコールを原料としたポリウレタン、ポリエステルは、優れた弾性体および耐加水分解性を有することから、工業的に重要な材料として広く用いられている。このポリテトラメチレンエーテルグリコールから得られるジグリシジルエーテルをビスフェノール型エポキシ樹脂の希釈剤として使用し、エポキシ硬化物の可撓性を向上させる方法が提案されている（特許文献２、特許文献３）。しかしこれらの方法は、硬化剤として可撓性に優れた直鎖状の脂肪族アミンや複素環のアミン類を用い、エポキシ硬化物の靭性改良を目的になされたものであり、ポリテトラメチレンエーテルグリコールのジグリシジルエーテルを主成分として用い、ゴム弾性を有する硬化物は得ている例は無い。 On the other hand, polyurethanes and polyesters made from polytetramethylene ether glycol as raw materials have been widely used as industrially important materials because they have excellent elastic bodies and hydrolysis resistance. A method has been proposed in which diglycidyl ether obtained from polytetramethylene ether glycol is used as a diluent for a bisphenol-type epoxy resin to improve the flexibility of an epoxy cured product (Patent Documents 2 and 3). However, these methods use linear aliphatic amines and heterocyclic amines with excellent flexibility as curing agents, and are intended to improve the toughness of epoxy cured products. There is no example in which a cured product having rubber elasticity using diglycidyl ether of glycol as a main component has been obtained.
そこで、エポキシ樹脂本来の優れた接着性を有しながら、ゴム弾性を有するエポキシ硬化物を得る方法が待たれていた。 Therefore, a method for obtaining an epoxy cured product having rubber elasticity while having excellent adhesiveness inherent to an epoxy resin has been awaited.
本発明は、上記問題点を解決し、ゴム弾性を有する硬化物を与えることができるエポキシ樹脂組成物およびエポキシ樹脂硬化体を提供しようとするものである。 The present invention is intended to solve the above problems and provide an epoxy resin composition and an epoxy resin cured product that can provide a cured product having rubber elasticity.
本発明は、以下の各発明を包含する。 The present invention includes the following inventions.
（１）（Ａ）成分；数平均分子量が２００〜２０００のポリテトラメチレンエーテルグリコールから得られるジグリシジルエーテル ５０〜１００質量％およびビスフェノール型エポキシ樹脂 ０〜５０質量％を含有する２５℃で液状のエポキシ樹脂
（Ｂ）成分；一分子中に芳香環を１個または脂環構造を１〜２個有する脂肪族ジアミン類及び／又はその変性物から選ばれるアミン系硬化剤
上記（Ａ）成分および（Ｂ）成分を配合してなるエポキシ樹脂組成物。
(1) Component (A): liquid at 25 ° C. containing 50-100% by mass of diglycidyl ether obtained from polytetramethylene ether glycol having a number average molecular weight of 200-2000 and 0-50% by mass of bisphenol type epoxy resin Epoxy resin (B) component; amine-based curing agent selected from aliphatic diamines having one aromatic ring or one or two alicyclic structures in one molecule and / or modified products thereof (A) and ( B) An epoxy resin composition comprising the component.
（２）（Ａ）成分中のポリテトラメチレンエーテルグリコールから得られるジグリシジルエーテルの含有量が６０〜１００質量％であることを特徴とする、前記（１）項に記載されたエポキシ樹脂組成物。 (2) The epoxy resin composition described in (1) above, wherein the content of diglycidyl ether obtained from polytetramethylene ether glycol in component (A) is 60 to 100% by mass. .
（３）（Ａ）成分中のポリテトラメチレンエーテルグリコールから得られるジグリシジルエーテルが、数平均分子量が２５０〜１５００のポリテトラメチレンエーテルグリコールから得られるジグリシジルエーテルであることを特徴とする、前記（１）又は（２）項に記載されたエポキシ樹脂組成物。 (3) The diglycidyl ether obtained from polytetramethylene ether glycol in component (A) is a diglycidyl ether obtained from polytetramethylene ether glycol having a number average molecular weight of 250 to 1500, The epoxy resin composition described in the item (1) or (2).
（４）（Ａ）成分中のビスフェノール型エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂及びビスフェノールF型エポキシ樹脂から選ばれる1種以上のエポキシ樹脂であることを特徴とする、前記（１）ないし（３）のいずれか1項に記載されたエポキシ樹脂組成物。 (4) The bisphenol type epoxy resin in the component (A) is at least one epoxy resin selected from bisphenol A type epoxy resin and bisphenol F type epoxy resin. The epoxy resin composition described in any one of (1).
（５）（Ｂ）成分中の脂肪族ジアミン類は、ｍ−キシリレンジアミン、イソホロンジアミン及び１,３−ビス（アミノメチル）シクロヘキサンから選ばれる1種以上のアミン類であることを特徴とする、前記（１）ないし（４）のいずれか1項に記載されたエポキシ樹脂組成物。 (5) The aliphatic diamine in component (B) is one or more amines selected from m-xylylenediamine, isophoronediamine and 1,3-bis (aminomethyl) cyclohexane. The epoxy resin composition according to any one of (1) to (4).
（６）（Ｂ）成分のアミン系硬化剤は、ｍ−キシリレンジアミン、イソホロンジアミンまたは１,３−ビス（アミノメチル）シクロヘキサンと、フェノール類、（メタ）アクリレート類、モノエポキシ化合物、スチレン類またはアクリロニトリルと反応させて得られる変性物であることを特徴とする、前記（１）ないし（５）のいずれか１項に記載されたエポキシ樹脂組成物。 (6) The amine curing agent of component (B) is m-xylylenediamine, isophoronediamine or 1,3-bis (aminomethyl) cyclohexane, phenols, (meth) acrylates, monoepoxy compounds, styrenes Alternatively, the epoxy resin composition described in any one of (1) to (5) above, which is a modified product obtained by reacting with acrylonitrile.
（７）（１）ないし（６）項のいずれかに１項に記載されたエポキシ樹脂組成物を硬化させて得られるＪＩＳ−Ｋ−６２５５のリュプケ式反発弾性率が２０〜９０％であるエポキシ樹脂硬化体。 (7) An epoxy having a rupture-type rebound resilience of JIS-K-6255 of 20 to 90% obtained by curing the epoxy resin composition described in any one of (1) to (6) Cured resin.
本発明のエポキシ樹脂組成物の硬化物はゴム弾性を有し、低温柔軟性、接着性に優れるため、シーリング剤、熱硬化型エラストマー用エポキシ樹脂組成物として有利に使用できる。 Since the cured product of the epoxy resin composition of the present invention has rubber elasticity and is excellent in low-temperature flexibility and adhesiveness, it can be advantageously used as a sealing agent and an epoxy resin composition for thermosetting elastomers.
（ポリテトラメチレングリコールのジグリシジルエーテル）
本発明のエポキシ樹脂組成物の（Ａ）成分におけるポリテトラメチレンエーテルグリコールのジグリシジルエーテルは、数平均分子量が２００〜２０００、好ましくは２５０〜１５００の範囲のポリテトラメチレンエーテルグリコールとエピクロルヒドリンを反応させることにより得ることができる。ポリテトラメチレングリコールの数平均分子量が２００未満であるとエポキシ硬化物の可撓性が低下し、２０００を越えると得られるジグリシジルエーテルが固体となり取り扱い性が悪くなるため好ましくない。
(Diglycidyl ether of polytetramethylene glycol)
The diglycidyl ether of polytetramethylene ether glycol in the component (A) of the epoxy resin composition of the present invention reacts polytetramethylene ether glycol and epichlorohydrin having a number average molecular weight in the range of 200 to 2000, preferably 250 to 1500. Can be obtained. When the number average molecular weight of the polytetramethylene glycol is less than 200, the flexibility of the epoxy cured product is lowered, and when it exceeds 2000, the resulting diglycidyl ether becomes a solid and the handling property is deteriorated.
本発明のエポキシ樹脂組成物に用いるポリテトラメチレンエーテルグリコールのジグリシジルエーテルは公知の製造方法を用いることにより得ることができる。例として、ポリテトラメチレンエーテルグリコールとエピクロルヒドリンを硫酸、三弗化ホウ素エチルエーテル、四塩化錫等の酸性触媒、または第４級アンモニウム塩類、第４級ホスホニウム塩類、クラウンエーテル類等の相間移動触媒の存在下に反応させ、クロルヒドリンエーテル体を製造し、次いで、このクロルヒドリンエーテル体を水酸化ナトリウム等の脱ハロゲン化水素剤と反応させて閉環せしめる２段階法により、ポリテトラメチレンエーテルグリコールのジグリシジルエーテルを得ることができる。 The diglycidyl ether of polytetramethylene ether glycol used in the epoxy resin composition of the present invention can be obtained by using a known production method. For example, polytetramethylene ether glycol and epichlorohydrin can be used in acidic catalysts such as sulfuric acid, boron trifluoride ethyl ether, and tin tetrachloride, or phase transfer catalysts such as quaternary ammonium salts, quaternary phosphonium salts, and crown ethers. In the presence of polytetramethylene ether glycol, a chlorohydrin ether is produced by reacting in the presence of the chlorohydrin ether and then ring-closing by reacting the chlorohydrin ether with a dehydrohalogenating agent such as sodium hydroxide. Of diglycidyl ether can be obtained.
（ビスフェノール型エポキシ樹脂）
本発明のエポキシ樹脂組成物の（Ａ）成分におけるビスフェノール型エポキシ樹脂は、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡ−アルキレンオキサイド付加体のジグリシジルエーテル、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＦのアルキレンオキサイド付加体のジグリシジルエーテル、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、テトラメチルビスフェノールＡ型エポキシ樹脂、テトラメチルビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＦ型エポキシ樹脂が挙げられ、これらの中で、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂が取り扱い性の面で好ましく、２５℃で液状のエポキシ樹脂が特に好ましい。
(Bisphenol type epoxy resin)
The bisphenol type epoxy resin in the component (A) of the epoxy resin composition of the present invention is bisphenol A type epoxy resin, diglycidyl ether of bisphenol A-alkylene oxide adduct, bisphenol F type epoxy resin, alkylene oxide adduct of bisphenol F. Diglycidyl ether, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, tetramethyl bisphenol A type epoxy resin, tetramethyl bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin Of these, bisphenol A-type epoxy resins and bisphenol F-type epoxy resins are preferable in terms of handleability, and liquid resins at 25 ° C. are particularly preferable.
前記のポリテトラメチレンエーテルグリコールのシ゛グリシジルエーテルおよびビスフェノール型エポキシ樹脂の使用割合は、ポリテトラメチレンエーテルグリコールのシ゛グリシジルエーテル ５０〜１００質量％に対し、ビスフェノール型エポキシ樹脂 ０〜５０質量％の割合であり、好ましくは各々6０〜１００質量％と０〜４０質量％であり、得られるエポキシ樹脂は２５℃液状であるのが好ましい。ビスフェノール型エポキシ樹脂が５０質量％を越えると、ゴム弾性を有する硬化物が得られないため好ましくない。 The polytetramethylene ether glycol diglycidyl ether and the bisphenol type epoxy resin are used in a proportion of 0 to 50% by mass of the bisphenol type epoxy resin with respect to 50 to 100% by mass of the polytetramethylene ether glycol diglycidyl ether. Yes, preferably 60 to 100% by mass and 0 to 40% by mass, respectively, and the obtained epoxy resin is preferably liquid at 25 ° C. If the bisphenol type epoxy resin exceeds 50% by mass, a cured product having rubber elasticity cannot be obtained, which is not preferable.
（アミン系硬化剤）
本発明のエポキシ樹脂組成物中におけるアミン系硬化剤は、一分子中に芳香環を１個または脂環構造を１〜２個有する脂肪族ジアミン類及び／又はその変性物から選ばれるアミン系硬化剤であり、エポキシ硬化物へ適度な硬度を付与し、かつ反発弾性率が大きくなるため好ましい。一分子中に芳香環が１個を越えるかまたは脂環構造が２個を越えるような脂肪族ジアミンは、硬化物が硬くなりすぎ柔軟性が無くなるため好ましくない。
また、トリエチレンテトラミンのような直鎖状の脂肪族ポリアミンは硬化物が柔らかくなりすぎ、反発弾性率が低下するため好ましくない。更に、ｍ−フェニレンジアミンのような芳香族ジアミン類はエポキシ樹脂との反応性が悪く、高温長時間硬化が必要なため、本組成物には好ましくない。
(Amine-based curing agent)
The amine-based curing agent in the epoxy resin composition of the present invention is an amine-based curing selected from aliphatic diamines having one aromatic ring or one to two alicyclic structures in one molecule and / or modified products thereof. It is preferable because it is an agent, imparts appropriate hardness to the epoxy cured product, and increases the resilience modulus. An aliphatic diamine having more than one aromatic ring or more than two alicyclic structures in one molecule is not preferable because the cured product becomes too hard and the flexibility is lost.
Further, a linear aliphatic polyamine such as triethylenetetramine is not preferable because the cured product becomes too soft and the rebound resilience decreases. Furthermore, aromatic diamines such as m-phenylenediamine are not preferred for the present composition because they have poor reactivity with epoxy resins and require high temperature and long time curing.
芳香環を１個有する脂肪族ジアミンの具体例としては、ｏ―キシリレンジアミン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミンが等挙げられ、ｍ−キシリレンジアミンが液体であるため取り扱い性の点で特に好ましい。また、脂環式を１〜２個有する脂肪族ジアミンは、イソホロンジアミン、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、１，２−シクロヘキシルジアミン、１，３−シクロヘキシルジアミン、１，４−シクロヘキシルジアミン、ノルボルナンジアミン、ビス（アミノメチル）トリシクロデカン、４,４’−メチレンビス（シクロヘキシルアミン）、４,４’−メチレンビス（２−メチルシクロヘキシルアミン）、４,４’−メチレンビス（２−エチル−６−メチルシクロヘキシルアミン）等が挙げられる。これらの中で一分子中に芳香環または脂環式を１個有する、ｍ−キシリレンジアミン、イソホロンジアミンまたは１,３−ビス（アミノメチル）シクロヘキサンが、本発明組成物中のエポキシ樹脂と反応性に優れ、優れた反発弾性率を有する硬化物が得られるという面で特に好ましい。 Specific examples of the aliphatic diamine having one aromatic ring include o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, and the like. Since m-xylylenediamine is a liquid, it is easy to handle. Particularly preferred in terms. Aliphatic diamines having 1 to 2 alicyclics are isophorone diamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,2-cyclohexyl diamine, 1, 3-cyclohexyldiamine, 1,4-cyclohexyldiamine, norbornanediamine, bis (aminomethyl) tricyclodecane, 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), 4 , 4′-methylenebis (2-ethyl-6-methylcyclohexylamine) and the like. Among these, m-xylylenediamine, isophoronediamine or 1,3-bis (aminomethyl) cyclohexane having one aromatic ring or alicyclic group in one molecule reacts with the epoxy resin in the composition of the present invention. It is particularly preferable in terms of obtaining a cured product having excellent properties and excellent impact resilience.
（変性アミン系硬化剤）
本発明に用いるアミン系硬化剤は、ｍ−キシリレンジアミン、イソホロンジアミン、1,3-ビス（アミノメチル）シクロヘキサンまたは４，４‘−メチレンビス（シクロヘキシルアミン）と、フェノール類（ホルムアルデヒド）、（メタ）アクリレート類、モノエポキシ類、スチレン類またはアクリロニトリルと反応させて変性させ用いるることができる。このような変性アミン系硬化剤は、アミンブラッシュ（アミン硬化剤が空気中の水分を吸収し白化する現象）を防止することができ、かつ皮膚刺激性も低下し取り扱い性が良くなるため好ましい。
アミン系硬化剤の変性方法は、ジアミン類1モルに対し、フェノール類とホルムアルデヒド、（メタ）アクリレート類、モノエポキシ化合物またはアクリロニトリルを０．１〜３モルの割合で、温度２０〜１５０℃、０．５〜１０時間の条件で縮合又は付加反応させることにより得ることができる。
(Modified amine curing agent)
The amine curing agent used in the present invention includes m-xylylenediamine, isophoronediamine, 1,3-bis (aminomethyl) cyclohexane or 4,4′-methylenebis (cyclohexylamine), phenols (formaldehyde), (meta ) It can be modified by reacting with acrylates, monoepoxies, styrenes or acrylonitrile. Such a modified amine-based curing agent is preferable because it can prevent amine brushing (a phenomenon in which the amine curing agent absorbs moisture in the air and whitens), and also reduces skin irritation and improves handling.
The modification method of the amine-based curing agent is such that phenol and formaldehyde, (meth) acrylates, monoepoxy compound or acrylonitrile at a ratio of 0.1 to 3 moles with respect to 1 mole of diamine, a temperature of 20 to 150 ° C., 0 It can be obtained by condensation or addition reaction under conditions of 5 to 10 hours.
本発明に用いるアミン系硬化剤の使用割合は、エポキシ樹脂のエポキシ当量により異なるが、好ましくはエポキシ樹脂１００質量部に対し、１０〜１５０質量部の範囲内で配合される。
上記範囲を外れると、エポキシ樹脂硬化物の可撓性及び耐湿性のバランスが悪くなるため好ましくない。
The proportion of the amine curing agent used in the present invention varies depending on the epoxy equivalent of the epoxy resin, but is preferably blended within a range of 10 to 150 parts by mass with respect to 100 parts by mass of the epoxy resin.
Outside the above range, the balance between flexibility and moisture resistance of the cured epoxy resin is deteriorated, which is not preferable.
（エポキシ樹脂硬化体）
本発明のエポキシ樹脂組成物は２０〜１５０℃の温度で、０．５〜２４時間の時間で熱硬化させることにより、ゴム弾性を有するエポキシ樹脂硬化体が得られ、このエポキシ樹脂硬化体は、ＪＩＳ−Ｋ−６２５５によるリュプケ式反発弾性率が２０〜９０％の範囲内である。反発弾性率が２０％未満であると、十分なゴム弾性を発揮できないため好ましくない。
(Hardened epoxy resin)
The epoxy resin composition of the present invention is thermally cured at a temperature of 20 to 150 ° C. for a time of 0.5 to 24 hours, whereby an epoxy resin cured body having rubber elasticity is obtained. The Lüpke-type rebound resilience according to JIS-K-6255 is in the range of 20 to 90%. A rebound resilience of less than 20% is not preferable because sufficient rubber elasticity cannot be exhibited.
（任意成分）
本発明のエポキシ樹脂組成物には、必要に応じて次の成分を添加配合することができる。
１）粉末状の補強剤や充填剤、たとえば酸化アルミニウム、酸化マグネシウムなどの金属酸化物、微粉末シリカ、溶融シリカ、結晶シリカなどのケイ素化合物、ガラスビーズ等のフィラー、水酸化アルミニウムなどの金属水酸化物、その他、カオリン、マイカ、石英粉末、グラファイト、二硫化モリブデン等。
これらの配合は、本発明のエポキシ組成物の透明性を損なわない範囲で配合され、本発明の組成物１００質量部に対して、１０〜１００質量部が適当である。
(Optional component)
In the epoxy resin composition of the present invention, the following components can be added and blended as necessary.
1) Powdery reinforcing agents and fillers, for example, metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, fillers such as glass beads, and metal water such as aluminum hydroxide Oxides, others, kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc.
These compounding is mix | blended in the range which does not impair the transparency of the epoxy composition of this invention, and 10-100 mass parts is suitable with respect to 100 mass parts of compositions of this invention.
２）着色剤又は顔料、たとえば二酸化チタン、モリブデン赤、紺青、群青、カドミウム黄、カドミウム赤及び有機色素等。
３）難燃剤、例えば、三酸化アンチモン、ブロム化合物及びリン化合物等。
これらは本発明のエポキシ樹脂組成物１００質量部に対して、０．０１〜３０質量部配合される。
2) Colorants or pigments such as titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red and organic dyes.
3) Flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds.
These are blended in an amount of 0.01 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin composition of the present invention.
４）さらに、エポキシ硬化物の性質を改善する目的で種々の硬化性モノマ−、オリゴマ−及び合成樹脂を配合することができる。たとえば、脂肪族モノエポキシ等のエポキシ樹脂用希釈剤、フッ素樹脂、アクリル樹脂、シリコ−ン樹脂等の１種又は２種以上の組み合わせを挙げることができる。これらの化合物及び樹脂類の配合割合は、本発明のエポキシ樹脂組成物の本来の性質を損なわない範囲の量、すなわち本発明の組成物１００質量部に対して、５０質量部以下が好ましい。 4) Furthermore, various curable monomers, oligomers and synthetic resins can be blended for the purpose of improving the properties of the epoxy cured product. For example, a diluent for epoxy resin such as aliphatic monoepoxy, one kind or a combination of two or more kinds such as fluororesin, acrylic resin, and silicone resin can be used. The compounding ratio of these compounds and resins is preferably 50 parts by mass or less with respect to an amount within a range that does not impair the original properties of the epoxy resin composition of the present invention, that is, 100 parts by mass of the composition of the present invention.
以下に、実施例及び比較例を挙げて本発明をさらに詳しく説明する。なお、例中の部は質量部を意味する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the part in an example means a mass part.
実施例１
数平均分子量が６５０のポリテトラメチレンエーテルグリコールとエピクロルヒドリンを反応することにより得られたポリテトラメチレンエーテルグリコールのジグリシジルエーテル（エポキシ当量；４４７ｇ／当量、２５℃における粘度；１９３ｍPa.s）８０部、ビスフェノール型樹脂としてエピコート８２８（ジャパンエポキシレジン社商品名；ビスフェノールＡ型エポキシ樹脂、エポキシ当量；１８６ｇ／当量）２０部、アミン系硬化剤としてｍ−キシリレンジアミン１０部を温度５０℃で均一になるまで混合しエポキシ樹脂組成物を得た。
この組成物を減圧下で脱泡した後、型の中に流し込み、オーブン中にて８０℃で３時間、次いで、１２０℃で３時間硬化し硬化物を得た。このエポキシ硬化物の物性値を表１に示す。
Example 1
80 parts of diglycidyl ether of polytetramethylene ether glycol obtained by reacting polytetramethylene ether glycol having a number average molecular weight of 650 and epichlorohydrin (epoxy equivalent: 447 g / equivalent, viscosity at 25 ° C .; 193 mPa.s), Epicoat 828 as a bisphenol type resin (Japan Epoxy Resin product name; bisphenol A type epoxy resin, epoxy equivalent; 186 g / equivalent) 20 parts, and 10 parts of m-xylylenediamine as an amine-based curing agent become uniform at a temperature of 50 ° C To obtain an epoxy resin composition.
After defoaming this composition under reduced pressure, it was poured into a mold and cured in an oven at 80 ° C. for 3 hours and then at 120 ° C. for 3 hours to obtain a cured product. The physical property values of this epoxy cured product are shown in Table 1.
実施例２〜５及び比較例１〜２
エポキシ樹脂、アミン系硬化剤を表１に示すように変える以外は、実施例１と同様の操作を行い、エポキシ樹脂組成物を得、硬化物を得た。エポキシ硬化物の物性値を表１に示す。
Examples 2-5 and Comparative Examples 1-2
Except changing the epoxy resin and the amine curing agent as shown in Table 1, the same operation as in Example 1 was performed to obtain an epoxy resin composition, and a cured product was obtained. Table 1 shows the physical properties of the epoxy cured product.
（註）
＊１ ；JIS-K-6255
＊２ ；JIS-K-6911
＊３ ；鉄-鉄の引っ張り接着剪断強度（JIS-K-6850）
＊４ ；厚さ3mm、直径50mmの円盤状硬化物の100℃、1時間煮沸後の吸水率
＊５ ；数平均分子量６５０の ホ゜リテトラメチレンエーテルク゛リコールから得られたジグリシジルエーテル
＊６ ；数平均分子量１０００の ホ゜リテトラメチレンエーテルク゛リコールから得られたジグリシジルエーテル
＊７ ；ビスフェノールA型エポキシ樹脂−WPE １８６（ジャパンエポキシレジン社製）
＊８ ；ビスフェノールＦ型エポキシ樹脂−WPE １６９（ジャパンエポキシレジン社製）
＊９ ；ｍ−キシリレンジアミン
＊１０；イソホロンジアミン
＊１１；１,３−ビス（アミノメチル）シクロヘキサン
＊１２；ｍ−キシリレンジアミン、ホルマリン及びフェノールをマンニッヒ反応させることにより得られた
アミン化合物（ジャパンエポキシレジン社製）
＊１３；トリエチレンテトラミン
(註)
* 1 JIS-K-6255
* 2: JIS-K-6911
* 3: Tensile bond shear strength of iron-iron (JIS-K-6850)
* 4; Water absorption after boiling for 1 hour at 100 ° C for a disk-shaped cured product with a thickness of 3 mm and a diameter of 50 mm * 5; Diglycidyl ether obtained from polytetramethylene ether glycol having a number average molecular weight of 650 * 6; Number average Diglycidyl ether obtained from polytetramethylene ether glycol having a molecular weight of 1000 * 7; bisphenol A type epoxy resin-WPE 186 (manufactured by Japan Epoxy Resin Co., Ltd.)
* 8; Bisphenol F type epoxy resin-WPE 169 (Japan Epoxy Resin Co., Ltd.)
* 9; m-xylylenediamine * 10; isophoronediamine * 11; 1,3-bis (aminomethyl) cyclohexane * 12; amine compound obtained by reacting m-xylylenediamine, formalin and phenol with Mannich reaction ( (Japan Epoxy Resin)
* 13: Triethylenetetramine
本発明のエポキシ樹脂組成物は、ゴム弾性を有する硬化体を与えるので、熱硬化型エラストマーとして有用である。 Since the epoxy resin composition of the present invention provides a cured product having rubber elasticity, it is useful as a thermosetting elastomer.
Claims (7)
（Ｂ）成分；一分子中に芳香環を１個または脂環構造を１〜２個有する脂肪族ジアミン類及び／又はその変性物から選ばれるアミン系硬化剤
上記（Ａ）成分および（Ｂ）成分を配合してなるエポキシ樹脂組成物。 Component (A): Epoxy resin liquid at 25 ° C. containing 50 to 100% by mass of diglycidyl ether obtained from polytetramethylene ether glycol having a number average molecular weight of 200 to 2000 and 0 to 50% by mass of bisphenol type epoxy resin ( Component B): Amine-based curing agent selected from aliphatic diamines having one aromatic ring or one to two alicyclic structures in one molecule and / or modified products thereof (A) and (B) An epoxy resin composition obtained by blending.
An epoxy resin cured product having a Lücke-type rebound resilience of JIS-K-6255 of 20 to 90% obtained by curing the epoxy resin composition according to any one of claims 1 to 6.
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| JP2007009158A (en) * | 2005-07-04 | 2007-01-18 | Japan Epoxy Resin Kk | Method for producing polyether glycol diglycidyl ether and epoxy resin composition |
| JP2008001758A (en) * | 2006-06-20 | 2008-01-10 | Sakamoto Yakuhin Kogyo Co Ltd | Novel oligomer-containing epoxy compound and curable epoxy resin composition using the same |
| JP2009149731A (en) * | 2007-12-19 | 2009-07-09 | Denki Kagaku Kogyo Kk | Electroconductive protection sheet |
| JP2010520924A (en) * | 2006-11-20 | 2010-06-17 | ダウ グローバル テクノロジーズ インコーポレイティド | Epoxy resin containing alicyclic diamine curing agent |
| JP2011252083A (en) * | 2010-06-02 | 2011-12-15 | Mitsui Chemicals Inc | Curing agent for epoxy resin, epoxy resin composition and epoxy resin cured product |
| JP2012046738A (en) * | 2010-07-29 | 2012-03-08 | Dainippon Printing Co Ltd | Adhesive composition and method of manufacturing thermosetting adhesive sheet |
| JP5294869B2 (en) * | 2006-10-31 | 2013-09-18 | 株式会社日本触媒 | Flexible optical waveguide and manufacturing method thereof |
| WO2016158871A1 (en) * | 2015-03-31 | 2016-10-06 | 三菱瓦斯化学株式会社 | Epoxy resin curing agent, epoxy resin composition, paint, civil engineering and construction member, hardened material and composite material, and method for producing epoxy resin curing agent |
| CN112225879A (en) * | 2020-10-19 | 2021-01-15 | 南昌航空大学 | Modified amine curing agent and preparation method thereof |
| CN114736486A (en) * | 2022-04-15 | 2022-07-12 | 安徽欣生防水工程有限公司 | High-elasticity modified resin grouting material and preparation method thereof |
| CN115433505A (en) * | 2022-09-20 | 2022-12-06 | 科顺民用建材有限公司 | Modified epoxy resin waterproof coating composition, modified epoxy resin waterproof coating, and preparation method and application thereof |
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| JP2007009158A (en) * | 2005-07-04 | 2007-01-18 | Japan Epoxy Resin Kk | Method for producing polyether glycol diglycidyl ether and epoxy resin composition |
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| JP2012046738A (en) * | 2010-07-29 | 2012-03-08 | Dainippon Printing Co Ltd | Adhesive composition and method of manufacturing thermosetting adhesive sheet |
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| CN112225879B (en) * | 2020-10-19 | 2023-03-10 | 南昌航空大学 | Modified amine curing agent and preparation method thereof |
| CN114736486A (en) * | 2022-04-15 | 2022-07-12 | 安徽欣生防水工程有限公司 | High-elasticity modified resin grouting material and preparation method thereof |
| CN115433505A (en) * | 2022-09-20 | 2022-12-06 | 科顺民用建材有限公司 | Modified epoxy resin waterproof coating composition, modified epoxy resin waterproof coating, and preparation method and application thereof |
| CN115521744A (en) * | 2022-11-04 | 2022-12-27 | 湖南工科固友科技发展有限公司 | Elastic epoxy adhesive and preparation method and application thereof |
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